CN117083352A - Low temperature curable clearcoat composition - Google Patents
Low temperature curable clearcoat composition Download PDFInfo
- Publication number
- CN117083352A CN117083352A CN202280025440.5A CN202280025440A CN117083352A CN 117083352 A CN117083352 A CN 117083352A CN 202280025440 A CN202280025440 A CN 202280025440A CN 117083352 A CN117083352 A CN 117083352A
- Authority
- CN
- China
- Prior art keywords
- polyester resin
- coating film
- composition
- range
- low temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000004645 polyester resin Substances 0.000 claims abstract description 74
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- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 33
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 28
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 26
- 239000012948 isocyanate Substances 0.000 claims abstract description 20
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- 239000008199 coating composition Substances 0.000 claims description 39
- 239000002253 acid Substances 0.000 claims description 16
- 230000009477 glass transition Effects 0.000 claims description 5
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 3
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- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- QVTWBMUAJHVAIJ-UHFFFAOYSA-N hexane-1,4-diol Chemical compound CCC(O)CCCO QVTWBMUAJHVAIJ-UHFFFAOYSA-N 0.000 description 2
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- UDSFAEKRVUSQDD-UHFFFAOYSA-N Dimethyl adipate Chemical compound COC(=O)CCCCC(=O)OC UDSFAEKRVUSQDD-UHFFFAOYSA-N 0.000 description 1
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- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
Abstract
The present invention relates to a low temperature curable clear coat composition comprising: an acrylic resin; a first polyester resin; a second polyester resin; and an isocyanate-based curing agent, wherein the first polyester resin has a hydroxyl number of 240 to 320mg KOH/g and the second polyester resin has a hydroxyl number of 100 to 180mg KOH/g.
Description
Technical Field
The present invention relates to a low temperature curable clear coating composition which is curable at low temperature, is low in manufacturing cost, and produces a coating film having excellent appearance characteristics.
Background
In general, a vehicle body outer panel should not develop deterioration and rust of a coating film, and should have durability to maintain the glossiness or color of the coating film. Therefore, the painting process of the vehicle is generally performed by subjecting the vehicle body to the electrodeposition painting after the pretreatment process, by subjecting the vehicle body to the intercoat to improve the adhesion and smoothness, and by subjecting the intercoat to the under painting to improve the aesthetic appearance of the vehicle body. Thereafter, in order to protect the color of the undercoat film, improve the appearance thereof, and protect the undercoat film from external influences, a clear coat film is generally coated.
As a conventional clear coat for automobiles, thermosetting coating compositions of resins containing hydroxyl groups and amino resins are widely used. However, when using the conventional thermosetting coating composition, appearance deterioration or deformation may occur when a part composed of a plastic material such as a bumper and a rear view mirror is cured under a high-temperature curing condition, and thus, there is an inconvenience in that the part is separated from a vehicle body and a separate coating process is performed. In addition, the color of the plastic material member, which is separated from the vehicle body and is coated separately, is different from the color of the vehicle body. Accordingly, low temperature curable clear coating compositions having a reduced curing temperature for performing a painting process in the case of integrating plastic material parts into a vehicle body are attracting attention.
As an alternative thereto, korean patent registration No. 1,655,621 (patent document 1) discloses a transparent coating composition comprising two acrylic polyol resins, a polyester polyol resin, a reactive silicon additive, and an isocyanate curing agent. However, since the mechanical properties of the coating film produced by the conventional low-temperature curable clear coating composition such as the clear coating composition of patent document 1 are insufficient, it can only be applied to repair or painting of parts, and there is a limit in application to car body painting.
Therefore, there is a need to research and develop a clear coating composition which can be cured at a low temperature of 120 ℃ or less, and a coating film produced therefrom has excellent mechanical properties, and thus is suitable for application to vehicle body painting.
Disclosure of Invention
Technical problem
The present invention provides a clear coating composition which can be cured at a low temperature of 120 ℃ or less and can produce a coating film having excellent mechanical properties.
Technical proposal
The present invention provides a low temperature curable clear coat composition comprising: acrylic resin, first polyester resin, second polyester resin, and isocyanate-based curing agent,
wherein the first polyester resin has a hydroxyl value of 240 to 320mg KOH/g, and
the second polyester resin has a hydroxyl number of 100 to 180mg KOH/g.
Advantageous effects
Since the clear coating composition according to the present invention can be cured at a low temperature of 120 ℃ or less and can reduce the energy cost of the coating process, it is economical, and since it can integrally coat a vehicle body and a material part attached to the vehicle body, it can prevent the problem of color difference between the coated part and the vehicle body. In addition, since both the vehicle body and the component can be coated by one coating process, inconvenience in process and cost loss can be reduced. In addition, since the coating film produced from the clear coating composition has excellent mechanical properties such as hardness, adhesion, water resistance, acid resistance, scratch resistance and solvent resistance, it is useful for vehicle body coating.
Detailed Description
Modes for carrying out the invention
The present invention will be described in detail below.
The "weight average molecular weight" and "number average molecular weight" used in the present specification are measured by a conventional method known in the art, and may be measured by a method of Gel Permeation Chromatography (GPC), for example.
In addition, the "glass transition temperature (Tg)" is measured by a method known in the art, and may be measured by a method of Differential Scanning Calorimetry (DSC), for example.
The values of the functional groups such as "acid value" and "hydroxyl value" may be measured by methods known in the art, and may represent, for example, values measured by titration or the like.
In addition, in the present specification, "(meth) acrylic acid" means "acrylic acid" and/or "methacrylic acid", and "(meth) acrylate" means "acrylate" and/or "methacrylate".
The low temperature curable clear coat composition according to the present invention comprises an acrylic resin, a first polyester resin, a second polyester resin, and an isocyanate-based curing agent.
Acrylic resin
Acrylic resins are used to impart film-forming and mechanical properties to the compositions.
As the acrylic resin, a product synthesized directly according to a known method may be used, or a commercially available product may be used. For example, the acrylic resin may be prepared by polymerizing one or more of a vinyl-based monomer and a (meth) acrylate-based monomer.
The kind of the vinyl-based monomer is not particularly limited, and for example, one or more selected from styrene, methyl styrene, dimethyl styrene, fluoro styrene, ethoxy styrene, methoxy styrene, phenylene vinyl ketone, vinyl t-butyl benzoate, vinyl cyclohexanoate, vinyl acetate, vinyl pyrrolidone, vinyl chloride, vinyl alcohol, acetoxystyrene, t-butyl styrene, and vinyl toluene may be used.
The (meth) acrylate-based monomer may include one or more selected from the group consisting of a (meth) acrylate-based monomer having no hydroxyl group and a (meth) acrylate monomer having a hydroxyl group.
The (meth) acrylate monomer having no hydroxyl group may include, for example, one or more selected from (meth) acrylic acid, meth) acrylic acid ester, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, isooctyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, isobornyl (meth) acrylate, and lauryl (meth) acrylate.
The hydroxyl group-containing (meth) acrylate monomer may be, for example, a hydroxyalkyl group-containing (meth) acrylate, and specifically may include one or more selected from the group consisting of 2-hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate.
For example, an acrylic resin may be produced using a radical polymerization method, and physical properties, i.e., weight average molecular weight (Mw), hydroxyl value (OHv), acid value (Av), etc., may be adjusted according to an initiator and polymerization time.
In addition, the acrylic resin may have a weight average molecular weight (Mw) of 10,000 to 40,000g/mol, 15,000 to 35,000g/mol, or 20,000 to 30,000 g/mol. When the weight average molecular weight of the acrylic resin is within this range, the hardness of the resulting coating film may be excellent. In addition, when the weight average molecular weight of the acrylic resin is less than the range, the molecular weight thereof is so small that the water resistance and chemical resistance of the resulting coating film are insufficient, and when the weight average molecular weight is more than the range, the viscosity increases with an increase in molecular weight, and the coating composition comprising the acrylic resin is inferior in processability and poor in leveling property, so that it may be difficult to produce a coating film having an excellent appearance.
In addition, the acrylic resin may have a hydroxyl value (OHv) of 100 to 200mg KOH/g or 145 to 170mg KOH/g. When the hydroxyl value of the acrylic resin is within this range, the effect of improving the weather resistance of the coating film is exhibited. In addition, when the hydroxyl value of the acrylic resin is less than this range, the formation of the coating film by the crosslinking reaction with the curing agent is insufficient, so that the hardness, water resistance, etc. of the coating film are deteriorated, and when it is more than this range, excessive curing occurs, so that the coating film becomes brittle and loses elasticity, and the appearance and weather resistance of the resulting coating film may be deteriorated.
The acrylic resin may have an acid value (Av) of 5 to 15mg KOH/g or 8 to 11mg KOH/g. When the acid value of the acrylic resin is within this range, the water dispersibility and storage stability of the coating composition can be improved and the water resistance can be improved. In addition, when the acid value of the acrylic resin is below this range, the curing reaction rate is reduced to deteriorate the appearance of the resulting coating film and the water-dispersion stability of the resin, and when it is above this range, the viscosity of the composition is increased to deteriorate the processability and water resistance of the coating film.
The acrylic resin may have a glass transition temperature (Tg) of 20 to 100 ℃, 40 to 70 ℃, or 52 to 58 ℃. When the glass transition temperature of the acrylic resin is within this range, the film-forming property and defoaming property of the composition and the gloss characteristics of the film are improved. In addition, when the glass transition temperature of the acrylic resin is lower than this range, the drying speed and crosslinking density of the coating film are reduced to deteriorate the impact resistance and water resistance of the resulting coating film, and when it is higher than this range, the coating film becomes brittle and its appearance and hardness may be lowered.
The acrylic resin may have a solids content (NV) of 60 to 80wt%, 65 to 75wt%, or 68 to 73wt% relative to the total weight of the resin. When the solid content of the acrylic resin is within this range, the storage stability of the resin and the storage stability of the coating composition may be improved and the workability may be excellent. In addition, when the solid content of the acrylic resin is below the range, the viscosity is too low, so that the workability of the coating composition comprising the resin becomes insufficient, and when it is above the range, the viscosity of the acrylic resin is too high, so that the stability during the reaction is poor, and the dispersion stability becomes poor, so that agglomeration may occur with the passage of time.
In addition, the acrylic resin may be included in an amount of 15 to 35wt% or 20 to 30wt% based on the total weight of the coating composition. When the acrylic resin is contained within this content range, the adhesion and impact resistance of the coating film can be improved. In addition, when the content of the acrylic resin is less than the range, the drying property is lowered, so that the adhesion strength and durability of the coating film are deteriorated, and when it is more than the range, the paint viscosity is increased to deteriorate the paint workability, paint fluidity and water repellency.
First polyester resin
The first polyester resin is used to form appearance characteristics and mechanical properties of a coating film produced by chemical bonding with an isocyanate-based curing agent.
As the first polyester resin, a product synthesized directly according to a known method may be used, or a commercially available product may be used. For example, the first polyester resin may be produced by reacting a first carboxylic acid and a first polyol.
Herein, the first carboxylic acid may be one or more selected from Adipic Acid (AA), isophthalic acid (IPA), trimellitic anhydride (TMA), alicyclic acid, phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, adipic acid, fumaric acid, maleic anhydride, tetrahydrophthalic anhydride (HHPA), hexahydrophthalic anhydride, and derivatives thereof.
The first polyol may be, for example, one or more selected from methoxypolyethylene glycol, 1, 6-hexanediol (1, 6-HD), neopentyl glycol (NPG), trimethylol propane (TMP), ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, 1, 4-hexanediol, and 3-methylene glycol.
The first polyester resin may have a hydroxyl number (OHv) of 240 to 320mg KOH/g or 260 to 290mg KOH/g. When the first polyester resin has a hydroxyl value in this range, the spreadability of the coating film is improved, and the chemical resistance by urethane reaction is improved. In addition, when the hydroxyl value of the first polyester resin is below the range, the crosslinking density with the isocyanate-based curing agent is insufficient, so that the durability and chemical resistance of the resulting coating film are deteriorated, and when it is above the range, over-curing occurs, so that the coating film becomes brittle, and the impact resistance and cold fracture resistance are deteriorated.
In addition, the first polyester resin may have a number average molecular weight (Mn) of 100 to 1,000g/mol, 200 to 900g/mol, or 300 to 800 g/mol. When the number average molecular weight of the first polyester resin is within this range, there is an effect of imparting smoothness to the paint and forming a soft coating film. When the number average molecular weight of the first polyester resin is less than the range, the molecular weight is small, so that the mechanical properties of the resulting coating film are deteriorated, and when it is more than the range, the fluidity is deteriorated due to the increase in the molecular weight, so that the appearance is deteriorated and the coating film becomes brittle, thereby deteriorating the cold fracture resistance (cold chipping resistance) and impact resistance.
The first polyester resin may have an acid value (Av) of 5 to 35mg KOH/g or 15 to 25mg KOH/g. When the acid value of the first polyester resin is within this range, rapid curing by heat treatment is prevented, thereby preventing poor appearance of the coating film and reducing occurrence of bursting. When the acid value of the first polyester resin is below this range, the curing reaction rate is reduced to deteriorate the hardness and appearance characteristics of the resulting coating film, and when it is above this range, the hydrophilicity is increased to deteriorate the water resistance.
In addition, the first polyester resin may have a solid content (NV) of 50 to 80wt% or 60 to 70 wt%. When the solid content of the first polyester resin is within this range, the content of the Total Volatile Organic Compound (TVOC) may be reduced due to the high solid content. When the solid content of the first polyester resin is below this range, the curing reactivity decreases due to the decrease in the solid content of the composition, and when it is above this range, poor workability of the resulting paint may occur to deteriorate the appearance.
In addition, the first polyester resin may be included in an amount of 5 to 15wt% or 8 to 12wt% based on the total weight of the coating composition. When the first polyester resin is contained within the content range, the appearance, scratch resistance, and coating film smoothness can be improved. When the content of the first polyester resin in the composition is below this range, the crosslinking density is reduced to deteriorate the mechanical properties and appearance, and when it is above this range, the viscosity of the composition may become too high to deteriorate the processability and drying property.
The composition may comprise the first polyester resin and the second polyester resin in a weight ratio of 1.5:1 to 2.5:1 or 1.8:1 to 2.2:1. The mixing weight ratio of the first polyester resin and the second polyester resin is within this range, and the durability and scratch resistance of the resulting coating film are improved. When the mixing weight ratio of the first polyester resin to the second polyester resin is below this range, i.e., the content of the first polyester resin is below the content of the second polyester resin, the crosslinking density of the resulting coating film is reduced to deteriorate the durability and scratch resistance, and when it is above this range, i.e., the content of the first polyester resin is above the content of the second polyester resin, the viscosity of the composition is increased to deteriorate the drying property and curing reactivity, thereby deteriorating the mechanical properties of the resulting coating film.
Second polyester resin
The second polyester resin serves to increase the solids content of the composition and improve the appearance, smoothness, scratch resistance and slip properties of the resulting coating film.
As the second polyester resin, a product synthesized directly according to a known method may be used, or a commercially available product may be used. For example, the second polyester resin may be produced by reacting a second carboxylic acid and a second polyol.
Herein, the second carboxylic acid may be one or more selected from Adipic Acid (AA), isophthalic acid (IPA), trimellitic anhydride (TMA), alicyclic acid, phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, adipic acid, fumaric acid, maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride (HHPA), isononanoic acid (INA), and derivatives thereof.
The second polyol may be one or more selected from 1, 6-hexanediol (1, 6-HD), pentaerythritol, sorbitol, methoxypolyethylene glycol, neopentyl glycol (NPG), trimethylol propane (TMP), ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, 1, 4-hexanediol, and 3-methylene glycol.
The second polyester resin may have a hydroxyl number (OHv) of 100 to 180mg KOH/g or 130 to 150mg KOH/g. When the second polyester resin has a hydroxyl value in this range, the spreadability of the coating film is improved, and the chemical resistance by urethane reaction is improved. In addition, when the hydroxyl value of the second polyester resin is below the range, the crosslinking density with the isocyanate-based curing agent is insufficient, so that the appearance, durability and chemical resistance of the resulting coating film are deteriorated, and when it is above the range, over-curing occurs, so that the coating film becomes brittle, and the coating workability and cold chipping resistance are deteriorated.
In addition, the second polyester resin may have a number average molecular weight (Mn) of 1,200 to 5,000g/mol, 1,300 to 4,500g/mol, or 1,500 to 4,000 g/mol. When the number average molecular weight of the second polyester resin is within this range, there are effects of paint smoothness and formation of a soft coating film. When the number average molecular weight of the second polyester resin is less than the range, the molecular weight is small, so that the mechanical properties of the resulting coating film are deteriorated, and when it is more than the range, the fluidity is deteriorated due to the increase in the molecular weight, so that the appearance is deteriorated and the coating film is hardened, thereby deteriorating the cold fracture resistance.
In addition, the second polyester resin may have an acid value (Av) of 10 to 40mg KOH/g or 20 to 30mg KOH/g. When the acid value of the second polyester resin is within this range, rapid curing by heat treatment is avoided, so that poor appearance of the coating film is prevented and occurrence of popping (popping) is reduced. When the acid value of the second polyester resin is below this range, the curing reaction rate is reduced to deteriorate the hardness and appearance characteristics of the resulting coating film, and when it is above this range, the hydrophilicity is increased to deteriorate the water resistance.
The second polyester resin may have a solid content (NV) of 60 to 80wt% or 65 to 75 wt%. When the solid content of the second polyester resin is within this range, the content of the Total Volatile Organic Compound (TVOC) may be reduced due to the high solid content. When the solid content of the second polyester resin is below this range, the solid content of the composition is reduced to deteriorate the curing reactivity, thereby deteriorating the mechanical properties of the resulting coating film, and when it is above this range, the workability of the resulting coating film is poor, thereby deteriorating the appearance characteristics of the coating film.
In addition, the second polyester resin may be included in an amount of 1 to 10wt% or 3 to 7wt% based on the total weight of the coating composition. When the second polyester resin is contained within the content range, the appearance, scratch resistance and coating film smoothness can be improved. When the content of the second polyester resin in the composition is below this range, the crosslinking density of the coating film is reduced to deteriorate the cold fracture resistance and scratch resistance, and when it is above this range, the viscosity of the composition may become too high to deteriorate the processability and drying properties, thereby deteriorating the appearance.
Isocyanate-based curing agents
The isocyanate-based curing agent reacts with the hydroxyl groups of the resin as described above to form urethane bonds, thereby curing the composition, thereby forming a coating film.
The type of the isocyanate-based curing agent is not particularly limited, and for example, the isocyanate-based curing agent may include an aliphatic polyisocyanate compound having no yellowness. Specifically, the isocyanate-based curing agent may include hexamethylene diisocyanate, isophorone diisocyanate, 4' -dicyclohexylmethane diisocyanate, tetramethylxylene diisocyanate, or a mixture thereof.
In addition, the isocyanate-based curing agent may have a content of unreacted isocyanate groups (NCO%) of 15 to 30wt% or 19 to 24wt%, relative to the total weight of the curing agent. When the nco% of the isocyanate-based curing agent is below this range, the crosslinking density of the coating film is reduced to deteriorate the impact resistance, water resistance and cold fracture resistance of the coating film, and when it is above this range, the curing rate is increased and the resin is agglomerated to deteriorate the appearance characteristics, gloss and mechanical characteristics of the coating film.
The isocyanate-based curing agent may be included in the composition in an amount of 20 to 35wt% or 24 to 29wt% based on the total weight of the coating composition. When the content of the isocyanate-based curing agent is below this range, the reactivity of the composition is insufficient, so that the crosslinking density becomes poor, so that the mechanical properties become poor, and when the content thereof is above this range, unreacted isocyanate groups appear in the cured coating film, so that the appearance and workability of the coating film become poor.
The clear coat composition may also comprise a solvent.
Solvent(s)
The solvent is used to adjust the viscosity of the composition, improve the drying properties, and improve the appearance characteristics and spreadability of the resulting coating film.
The solvent is not particularly limited as long as it is commonly used in a clear coating composition, and for example, may include one or more selected from an aromatic solvent, an acetate-based solvent, an alcohol-based solvent, and a propionate-based solvent. Specifically, the solvent may include aromatic solvents 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, methyl glutarate, methyl succinate, methyl adipate, dimethyl glutarate, dimethyl succinate, dimethyl adipate, propylene glycol methyl ether acetate (PMA), butyl carbitol acetate, and butyl cellosolve acetate; alcohol-based solvents such as n-butanol, propanol, 1-methoxy-2-propanol and 2-butoxyethanol; ketone-based solvents such as acetone, methyl ethyl ketone, methyl butyl ketone, and methyl isobutyl ketone; propionate-based solvents such as ethyl ethoxypropionate and the like. In addition, commercial products of the aromatic solvent may include kocosol#100, kocosol#150, and the like.
In addition, the solvent may be included in the composition in an amount of 15 to 45wt% or 25 to 35wt% based on the total weight of the coating composition. When the solvent is contained within this range, the viscosity of the composition is appropriately adjusted to improve the processability and the drying property.
Additive agent
The clearcoat composition according to the invention may also contain additives such as curing catalysts, UV absorbers, surface smoothing agents and flow modifiers. Herein, the additive is not particularly limited as long as it is generally added to the coating composition.
In addition, the content of the additive is not particularly limited as long as it is generally contained in the clear coating composition. For example, the additives may be included in the coating composition in an amount of 1 to 10wt% or 3 to 7wt% based on the total weight of the coating composition.
Two-pack type coating composition
The clear coating composition may be a two-part coating composition comprising a main part and a curing agent part. For example, the clearcoat composition can include a main portion including an acrylic resin, a first polyester resin, a second polyester resin, a solvent, and an additive, and a curative portion including an isocyanate-based curative. In addition, the clear coat composition may be used after the main part and the curing agent part are mixed before application.
The clear coat composition may have a solids content of 40 to 60wt% or 45 to 55 wt%. When the solid content of the clear coat composition is within this range, the coating workability of the composition may become suitable.
The clear coat composition may be cured at 60 ℃ to 120 ℃, 70 ℃ to 110 ℃, or 80 ℃ to 110 ℃. Since the clear coat composition is curable in this temperature range, the cost required for the coating process can be reduced, and thus it is economical, and since it can integrally coat the vehicle body and the material parts attached thereto, it is possible to prevent the problem of the color of the coated parts from being different from that of the vehicle body. In addition, since both the vehicle body and the component can be coated by one coating process, inconvenience in the process and cost loss can be reduced.
The clear coating composition may have a viscosity of 40 to 70 seconds or 50 to 60 seconds based on Ford Cup No.4 at 25 ℃. When the viscosity of the clear coating composition at 25 ℃ is lower than this range, problems such as downward flow in a vertical plane may occur, and when it is higher than this range, the viscosity of the composition is so high that the appearance characteristics of the resulting coating film become poor or a load is applied to the coater to cause the coater to malfunction.
Since the clear coating composition according to the present invention as described above can be cured at a low temperature of 120 ℃ or less and can reduce the cost of the coating process, it is economical and since it can integrally coat a vehicle body and a material part attached to the vehicle body, it can prevent the problem of color difference between the coated part and the vehicle body. In addition, since both the vehicle body and the component can be coated by one coating process, inconvenience in the process and cost loss can be reduced. In addition, since the coating film produced from the clear coating composition has excellent mechanical properties such as hardness, adhesion, water resistance, acid resistance, scratch resistance and solvent resistance, it is useful for vehicle body coating.
Best mode for carrying out the invention
Hereinafter, the present invention will be described in more detail by the following examples. However, the following examples are only for aiding in the understanding of the present invention, and the scope of the present invention is not limited thereto in any way.
Examples 1 to 15 and comparative examples 1 to 7: preparation of clear coat composition
The components were mixed at the contents in tables 1 to 3 to prepare a clear coating composition having a viscosity of 55 seconds at 25 ℃ based on ford cup No. 4.
TABLE 1
TABLE 2
TABLE 3
The manufacturers, product names, component names, and the like used in the comparative examples and examples are shown in table 4 below.
TABLE 4
Experimental example: evaluation of film Properties
A top coat paint (manufacturer: KCC, product name: WT 3090) was applied to the sample and dried to form a top coat film having a thickness of 15. Mu.m. Then, the clear coat compositions produced in examples and comparative examples were applied on top coat films and cured at 100℃for 25 minutes to form clear coat films having a thickness of 40. Mu.m, thereby producing finished coating films. The physical properties of the samples were measured, and the results are shown in table 5.
Specifically, a manual spray gun (nozzle caliber: 1.5mm, air pressure: kept constant at 4.5kgf/cm was used 2 Left or right) is coated with the clear coat film while keeping the distance between the nozzle opening and the sample constant at 30cm and moving horizontally at a speed of 40 to 50 cm/sec.
(1) Workability in painting
When the paint was sprayed with a manual spray gun, the clear coat compositions of examples and comparative examples were applied back and forth twice, and the degree of atomization, smoothness and thick paste application ability of the paint during the application were compared.
Specifically, the paint spreadability on the surface was good and the thick paste paint ability was excellent, and the paint workability was evaluated as excellent (excellent); when the coating workability was evaluated as good (good) by visual inspection, the thick paste coating ability was good but the paint spreadability was insufficient; the coating workability was evaluated as general (. DELTA.) when the visual inspection was carried out, the thick paste coating ability and the coating spreadability were insufficient and the number of occurrence of the foreign matters of the coating was less than 3, and the coating workability was evaluated as poor (X) when the number of occurrence of the foreign matters of the coating was 3 or more and shrinkage cavity occurred.
(2) Appearance of
The gloss (LU), sharpness (SH), and Orange Peel (OP) of the resultant finished coating film were measured using a vehicle exterior appearance Wave Scan DOI (BYK Gardner), and using the measured physical properties, a comprehensive appearance evaluation value (CF) was calculated by the following equation 1.
[ mathematical formula 1]
CF＝LU×0.15+SH×0.35+OP×0.5
At this time, CF was measured and calculated laterally and longitudinally.
When the calculated CF was 65 or more, the appearance was evaluated as excellent (very good), when the CF was 60 or more and less than 65, the appearance was evaluated as good (o), when the CF was 55 or more and less than 60, the appearance was evaluated as general (Δ), and when the CF was less than 55, the appearance was evaluated as poor (x).
(3) Gloss level
The 20 ° glossiness of the coated sample was measured using a glossmeter, and 20 ° glossiness of 90 or higher was evaluated as excellent (excellent), 20 ° glossiness of 85 or higher and less than 90 was evaluated as good (o), 20 ° glossiness of 80 or higher and less than 85 was evaluated as general (Δ), and 20 ° glossiness of less than 80 was evaluated as poor (x).
(4) Recoating adhesion
The top coat film and the clear coat film were all removed, the top coat paint and the clear coat composition were applied in the same manner as described above, and the recoating adhesion was evaluated by the checkerboard method.
Specifically, in the checkerboard method, the surface of the clear coat film was cut into 100 squares of 2mm wide by 2mm high with a knife, and these squares were peeled off using an adhesive tape to measure the adhesion. At this time, when 100 squares are 100% fully attached, the measured adhesion is evaluated as excellent (excellent), when 70% or more and less than 100% of squares are retained, the measured adhesion is evaluated as good (o), when 50% or more and less than 70% of squares are retained, the measured adhesion is evaluated as general (Δ), and when less than 50% of squares are retained, the measured adhesion is evaluated as poor (x).
(5) Impact resistance
Impact resistance of the coated samples was evaluated according to ASTM D2794. At this time, using a DuPont impact tester, 500g of a weight was dropped onto the sample while changing the drop height of the weight from 30cm to 50cm, and the appearance of the coating film was observed. As an observation result, when no crack and peeling occurred on the topcoat film at a weight drop height of 50cm, the impact resistance was evaluated as excellent (verygood), when the drop height was 40cm or more and less than 50cm, the impact resistance was evaluated as good (good), when the drop height was 30cm or more and less than 40cm, the impact resistance was evaluated as general (. DELTA.), and when the drop height was less than 30cm, the impact resistance was evaluated as poor (×).
(6) Water resistance
The finished coating film was immersed in a constant temperature water bath at 40℃for 240 hours, allowed to stand at room temperature for 1 hour, and then the adhesion was evaluated in the same manner as in the checkerboard method of item (4), and the evaluation criteria were applied identically.
(7) Paint fluidity
The samples of the top coat film formed on the steel sheet having the holes of 5mm in diameter were hung vertically, the clear coat compositions of examples and comparative examples were coated in the same manner as described above, and dried and cured, and the surfaces of the resulting coating films were observed to evaluate the paint fluidity of the compositions.
Specifically, the paint form of the lower part of the hole was observed, and the thickness of the coating film at the starting point where the occurrence of flow was observed was recorded as the flow limit film thickness. At this time, the lower the value of the flow limit film thickness measured, the insufficient paint fluidity was considered. At this time, when the flow limit film thickness is 40 μm or more, the paint fluidity is evaluated to be excellent (excellent), when the flow limit film thickness is 35 μm or more and less than 40 μm, the paint fluidity is evaluated to be good (o), when the flow limit film thickness is 30 μm or more and less than 35 μm, the paint fluidity is evaluated to be general (Δ), and when the flow limit film thickness is less than 30 μm, the paint fluidity is evaluated to be poor (x).
(8) Resistance to cold cracking
A coated sample having a size of 150mm by 70mm was left to stand at-20.+ -. 3 ℃ for 3 hours, and cold fracture resistance was measured using a fracture resistance tester (manufacturer: stone chip resistance tester, model name: SAE J400). Specifically, 50g of crushed stone (diameter: 4 mm) was sprayed onto the finished paint at an angle of 45℃at a pressure of 4 bar. Then, the sample was taken out, and foreign matter remaining in the coating film, such as a peeled coating film, was removed with a cellophane tape.
At this time, when the damaged area of the finished coating film is 1mm or less, cold chipping resistance is evaluated to be excellent (good), when the damaged area is greater than 1mm and equal to or less than 2mm, cold chipping resistance is evaluated to be good (good), when the damaged area is greater than 2mm and equal to or less than 3mm, cold chipping resistance is evaluated to be general (. DELTA.), and when the damaged area is greater than 3mm, cold chipping resistance is evaluated to be poor (×).
TABLE 5
As can be seen from table 5, the composition of the example had better coating workability and paint fluidity than the composition of the comparative example, and the coating film produced from the composition of the example had appearance, glossiness, recoating adhesion, impact resistance, and cold crack resistance superior to those of the coating film of the comparative example.
Furthermore, the coating film of comparative example 1 comprising the first polyester resin-4 having a low hydroxyl value and the coating film of comparative example 3 comprising the second polyester resin-4 having a low hydroxyl value were insufficient in impact resistance, water resistance and cold fracture resistance. In particular, the appearance characteristics of the coating film of comparative example 3 were insufficient.
In addition, the appearance characteristics, gloss and cold fracture resistance of the coating film of comparative example 2 containing the first polyester resin-5 having a high hydroxyl value and the coating film of comparative example 4 containing the second polyester resin-5 having a high hydroxyl value were insufficient. In particular, the impact resistance of the coating film of comparative example 2 was also insufficient, while the coating workability of the composition of comparative example 4 was insufficient.
The appearance characteristics, recoating adhesion, impact resistance, water resistance, and cold crack resistance of the coating film of comparative example 5 containing no acrylic resin were insufficient.
In addition, the composition of comparative example 5, which contained only one second polyester resin and no first polyester resin, was insufficient in paint fluidity, and the appearance characteristics, impact resistance, and cold crack resistance of the coating film produced therefrom were insufficient.
The coating film of comparative example 7, which contained only one first polyester resin and no second polyester resin, was insufficient in gloss, impact resistance, water resistance, and cold fracture resistance.
Claims (6)
1. A low temperature curable clear coat composition comprising: acrylic resin, first polyester resin, second polyester resin, and isocyanate-based curing agent,
wherein the first polyester resin has a hydroxyl value of 240 to 320mg KOH/g and
the second polyester resin has a hydroxyl number of 100 to 180mg KOH/g.
2. The low temperature curable clear coating composition of claim 1, wherein the acrylic resin has a weight average molecular weight of 10,000 to 40,000g/mol, a hydroxyl number of 100 to 200mg KOH/g, an acid number of 5 to 15mg KOH/g, and a glass transition temperature of 20 to 100 ℃.
3. The low temperature curable clear coating composition of claim 1,
wherein the first polyester resin has a number average molecular weight of 100 to 1,000g/mol, and
the second polyester resin has a number average molecular weight of 1,200 to 5,000 g/mol.
4. The low temperature curable clear coating composition of claim 1, wherein the first polyester resin and the second polyester resin are included in a weight ratio of 1.5:1 to 2.5:1.
5. The low temperature curable clear coating composition of claim 1, wherein the isocyanate-based curing agent has an unreacted isocyanate group content of 15 to 30wt% relative to the total weight of the curing agent.
6. The low temperature curable clear coating composition of claim 1, wherein the acrylic resin is included in an amount of 15 to 35wt%, the first polyester resin is included in an amount of 5 to 15wt%, the second polyester resin is included in an amount of 1 to 10wt%, and the isocyanate-based curing agent is included in an amount of 20 to 35wt%, based on the total weight of the coating composition.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020210042976A KR102567438B1 (en) | 2021-04-01 | 2021-04-01 | Clear coat composition for low temperature curing |
| KR10-2021-0042976 | 2021-04-01 | ||
| PCT/KR2022/004289 WO2022211399A1 (en) | 2021-04-01 | 2022-03-28 | Low-temperature curing type clear coat composition |
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| CN117083352A true CN117083352A (en) | 2023-11-17 |
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| CN202280025440.5A Pending CN117083352A (en) | 2021-04-01 | 2022-03-28 | Low temperature curable clearcoat composition |
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| KR (1) | KR102567438B1 (en) |
| CN (1) | CN117083352A (en) |
| WO (1) | WO2022211399A1 (en) |
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| KR101052223B1 (en) * | 2009-11-30 | 2011-07-27 | 유한회사 피피지코리아 | Dual Curing Two-Component Clear Coat Composition for Automotive |
| JP2015038162A (en) * | 2010-04-20 | 2015-02-26 | 日本ビー・ケミカル株式会社 | Polyester resin and application of the same |
| KR101655621B1 (en) | 2014-12-18 | 2016-09-07 | 현대자동차주식회사 | A clear coat composition with antipollution |
| KR102567352B1 (en) * | 2018-09-07 | 2023-08-16 | 주식회사 케이씨씨 | Clear paint composition |
| KR102229058B1 (en) * | 2018-12-21 | 2021-03-18 | 주식회사 케이씨씨 | Top coat composition |
| KR102242958B1 (en) * | 2018-12-31 | 2021-04-21 | 주식회사 케이씨씨 | Clear coat composition |
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2021
- 2021-04-01 KR KR1020210042976A patent/KR102567438B1/en active IP Right Grant
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- 2022-03-28 CN CN202280025440.5A patent/CN117083352A/en active Pending
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| KR102567438B1 (en) | 2023-08-16 |
| KR20220136819A (en) | 2022-10-11 |
| WO2022211399A1 (en) | 2022-10-06 |
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