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
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/02—Emulsion paints including aerosols
  • C09D5/024—Emulsion paints including aerosols characterised by the additives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
  • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
  • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
• • 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
  • C09D7/43—Thickening agents
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
  • B05D7/50—Multilayers
  • B05D7/52—Two layers
  • B05D7/53—Base coat plus clear coat type

Definitions

• the present disclosure relates to an aqueous colored coating composition and a method for forming a multilayer coating using the aqueous colored coating composition.
• Patent Document 1 describes a precision film-forming resin that includes a film-forming resin dispersed in an aqueous medium, a crosslinking agent capable of crosslinking with the film-forming resin, a rheology modifier, a coloring agent, and a swelling solvent that swells the film-forming resin.
• a coating composition for painting is disclosed (claim 1), wherein the solids content of the coating composition is less than 25% by weight, based on the total weight of the coating composition.
• the coating composition according to Patent Document 1 has room for improvement in the ejection stability of the coating composition, the sagging of the coating film formed from the coating composition, and the like. Therefore, the present disclosure provides excellent discharge stability and sag resistance of the formed coating film in coating using a liquid discharge head that controls discharge by changing the relative distance between a valve body and a discharge port.
• the purpose of the present invention is to provide a water-based colored paint composition having excellent properties and sharpness.
• the present disclosers provide a water-based colored paint composition that is coated using a liquid ejection head that controls ejection by changing the relative distance between a valve body and a discharge port, the water-based colored paint composition described above.
• the viscosity (V 1 ) is 20 to 100 mPa ⁇ s at a temperature of 23°C and a shear rate of 1,000 sec -1
• the viscosity (V 1 ) of 5,000 to 40,000 mPa ⁇ s at a temperature of 23°C and a shear rate of 0.1 sec -1.
• V 2 aqueous colored coating composition having (V 2 ).
• the water-based colored paint composition of the present disclosure has excellent ejection stability in coating using a liquid ejection head that controls ejection by changing the relative distance between the valve body and the ejection port, and the coating composition that is formed Excellent film sag resistance and image clarity.
• An aqueous colored paint composition that is applied using a liquid discharge head that controls discharge by changing the relative distance between a valve body and a discharge port, the composition comprising:
• the water-based colored coating composition has a viscosity (V 1 ) of 20 to 100 mPa ⁇ s at a temperature of 23°C and a shear rate of 1,000 sec -1 and a viscosity (V 1 ) of 5,000 to 40 mPa ⁇ s at a temperature of 23°C and a shear rate of 0.1 sec -1 . ,000 mPa ⁇ s of viscosity (V 2 ), Water-based colored paint composition.
• the aqueous colored coating composition has a predetermined viscosity (V 1 ) and therefore has excellent discharge stability.
• V 1 a predetermined viscosity
• the thickness of the coating film formed from the water-based colored paint composition may become uneven, resulting in poor smoothness, color reproducibility, etc. , and the coating performance may be poor.
• V 2 a predetermined viscosity
• the water-based colored paint composition satisfies formula (1), the viscosity (V 4 ) at the shear rate when ejected from the liquid ejection head is low, and the water-based colored paint composition is controlled from the liquid ejection head. The smaller size makes it easier to dispense and has excellent dispensing stability.
• the water-based colored paint composition satisfies formula (2), the water-based colored paint composition attached to the object has a high viscosity (V 5 ) at a shear rate corresponding to sagging, and the water-based colored paint composition has a high viscosity (V 5 ) at a shear rate corresponding to sagging.
• the coating film formed from the coating composition has excellent sagging resistance.
• aqueous colored coating composition according to any one of aspects 1 to 4, wherein the aqueous colored coating composition contains an acrylic resin emulsion (A) and a viscosity modifier (B). Since the water-based colored paint composition contains the acrylic resin emulsion (A) and the viscosity modifier (B), the coating film formed from the water-based colored paint composition has excellent sagging resistance.
• Step 1 Applying the water-based colored paint composition according to any one of aspects 1 to 5 using a liquid discharge head that controls discharge by changing the relative distance between the valve body and the discharge port. forming a colored coating film on the object to be coated by discharging it close to the object;
• Step 2 a step of applying a clear paint composition to the colored paint film to form a clear paint film, A method for forming a multilayer coating film.
• the above method for forming a multilayer coating film has excellent discharge stability of the aqueous colored coating composition, and excellent sagging resistance of the coating film formed from the aqueous colored coating composition.
• the multilayer coating film has excellent image clarity because the colored coating film has a predetermined dry film thickness.
• the water-based colored coating composition of the present disclosure and the method for forming a multi-layer coating film using the water-based colored coating composition (hereinafter may simply be referred to as the "method for forming a multi-layer coating film") will be described in detail below. explain.
• the water-based colored paint composition of the present disclosure is applied using a liquid ejection head that controls ejection by changing the relative distance between the valve body and the ejection port.
• the liquid ejection head that controls ejection by changing the relative distance between the valve element and the ejection port may be used, for example, by reducing the relative distance between the valve element and the ejection port.
• Examples include those that discharge an aqueous colored paint composition, and those that discharge an aqueous colored coating composition by increasing the relative distance between the valve body and the discharge port.
• liquid ejection head examples include an on-demand type (for example, a piezo type, a thermal type, a valve type), a continuous type, and the like, and the on-demand type, particularly the piezo type, is preferable. This is because the high viscosity water-based colored coating composition has excellent discharge properties.
• the piezo type liquid ejection head examples include a piezo jet dispenser and X JET (high viscosity liquid compatible model) manufactured by SSI JAPAN.
• the water-based colored coating composition has a viscosity (V 1 ) of 20 to 100 mPa ⁇ s, preferably 30 to 60 mPa ⁇ s, and more preferably 45 to 60 mPa ⁇ s at a temperature of 23°C and a shear rate of 1,000 sec -1 . has. Thereby, the water-based colored coating composition has excellent ejection stability from the liquid ejection head.
• V 1 viscosity
• the aqueous colored coating composition has a viscosity (V2) of 5,000 to 40,000 mPa ⁇ s, preferably 11,000 to 35,000 mPa ⁇ s, and more preferably 25,000 to 30,000 mPa ⁇ s at a temperature of 23° C. and a shear rate of 0.1 sec ⁇ 1 , which provides the aqueous colored coating composition with excellent discharge stability and the coating film formed from the aqueous colored coating composition with excellent sagging resistance.
• V2 viscosity
• the water-based colored coating composition has a tan ⁇ (loss elasticity modulus/storage modulus).
• tan ⁇ loss elasticity modulus/storage modulus
• the aqueous colored coating composition has excellent ejection stability, and the coating film formed from the aqueous coating composition has excellent image clarity. Note that methods for measuring viscosity (V 1 ), viscosity (V 2 ), and tan ⁇ will be explained in Examples.
• the water-based colored paint composition has a viscosity (V 3 ) after being held at a shear rate of 0.1 sec -1 for 50 seconds at a temperature of 23°C, and a shear rate of 1,000 sec -1 ,
• V 4 /V 3 is preferably 0. 001, more preferably greater than 0.002, and even more preferably greater than 0.003, and preferably less than 0.007, more preferably less than 0.006, and even more preferably less than 0.005.
• the viscosity (V 4 ) at the shear rate when ejected from the liquid ejection head is low, making it easier to eject the water-based colored paint composition from the liquid ejection head in a controlled size. Excellent discharge stability.
• V 5 /V 4 is preferably greater than 30, more preferably greater than 50, and still more preferably greater than 60, and preferably less than 200, more preferably less than 180, and even more preferably less than 160.
• V 5 the aqueous colored coating composition adhered to the object to be coated has a high viscosity (V 5 ) at a shear rate corresponding to sag, and the coating film formed from the aqueous colored coating composition has excellent sagging resistance. Note that methods for measuring viscosity (V 3 ), viscosity (V 4 ), and viscosity (V 5 ) will be explained in Examples.
• the above water-based colored coating composition preferably has a solid content concentration of 10 to 25% by mass, more preferably 10 to 20% by mass, and even more preferably 10 to 16% by mass.
• the aqueous colored coating composition has excellent ejection stability, and the coating film formed from the aqueous coating composition has excellent image clarity.
• the solid content concentration is determined by measuring the object to be measured (for example, a water-based colored paint composition) into a heat-resistant container such as an aluminum foil cup, spreading the object to be measured on the bottom of the container, and heating the object at 110°C. Dry for 1 hour, weigh the mass of the components in the measurement target that remain after drying, and determine the ratio of the mass of the components in the measurement target that remain after drying to the total mass of the measurement target before drying. It can be calculated by measuring the object to be measured (for example, a water-based colored paint composition) into a heat-resistant container such as an aluminum foil cup, spreading the object to be measured on the bottom of the container, and heating the object at 110°C. Dry for 1 hour, weigh the mass of the components in the measurement target that remain after drying, and determine the ratio of the mass of the components in the measurement target that remain after drying to the total mass of the measurement target before drying. It can be calculated by
• the water-based colored paint composition is not particularly limited in its composition as long as it has the above-mentioned viscosity, but resins such as acrylic resins, polyester resins, alkyd resins, polyurethane resins, epoxy resins, silicone resins, etc. Any combination etc. can be included.
• the resin can be an emulsion, and can include, for example, an acrylic resin emulsion, a polyester resin emulsion, an alkyd resin emulsion, a polyurethane resin emulsion, an epoxy resin emulsion, a silicone resin emulsion, any combination thereof, and the like.
• the resin preferably includes an acrylic resin emulsion (acrylic resin emulsion (A)).
• the acrylic resin emulsion (A) is formed by emulsifying and dispersing an acrylic resin in an aqueous medium, and includes, for example, an emulsion produced by emulsion polymerization of a polymerizable unsaturated monomer mixture.
• the acrylic resin emulsion (A) is particularly preferably a core-shell type emulsion consisting of a core part made of copolymer (I) and a shell part made of copolymer (II), and furthermore, copolymer (I) is preferably A product obtained by copolymerizing a polymerizable unsaturated monomer (a1) having two or more polymerizable unsaturated groups and a polymerizable unsaturated monomer (a2) other than the polymerizable unsaturated monomer (a1). It is desirable that the copolymer (II) be obtained by copolymerizing a plurality of polymerizable unsaturated monomers (a3) from the viewpoint of improving the appearance and water resistance of the resulting coating film.
• Examples of the polymerizable unsaturated monomer (a1) include ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, and 1,6-hexanediol di(meth)acrylate. , allyl(meth)acrylate, divinylbenzene, trimethylolpropane triacrylate, methylenebis(meth)acrylamide, ethylenebis(meth)acrylamide, and combinations thereof.
• “(meth)acrylate” means acrylate and/or methacrylate.
• the polymerizable unsaturated monomer (a2) other than the polymerizable unsaturated monomer (a1) (hereinafter sometimes simply referred to as "polymerizable unsaturated monomer (a2)") is the same as the polymerizable unsaturated monomer (a1). It is a monomer having one copolymerizable polymerizable unsaturated group in one molecule, and examples of the polymerizable unsaturated group include compounds having a vinyl group, a (meth)acryloyl group, etc.
• polymerizable unsaturated monomer (a2) examples include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, Isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-hexyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, tridecyl (meth)acrylate, Lauryl (meth)acrylate, stearyl (meth)acrylate, isostearyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name), cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, t-butyl
• Alkyl (meth)acrylate Polymerizable unsaturated monomers having fluorinated alkyl groups such as fluoroolefins; Monomers having photopolymerizable functional groups such as maleimide groups; N-vinylpyrrolidone, ethylene, butadiene, chloroprene, vinyl propionate, Vinyl compounds such as vinyl acetate; Carboxyl group-containing polymerizable unsaturated monomers such as (meth)acrylic acid, maleic acid, crotonic acid, ⁇ -carboxyethyl acrylate; (meth)acrylonitrile, (meth)acrylamide, N,N-dimethyl Nitrogen-containing polymerizable unsaturated monomers such as aminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylamide, adducts of glycidyl (meth)acrylate and amines; 2-hydroxyethyl (meth)acrylate monomers of (
• the polymerizable unsaturated monomer (a1) is preferably 0.1 to
• the range of the polymerizable unsaturated monomer (a2) is preferably 20% by mass, more preferably 0.2 to 10% by mass, and even more preferably 0.7 to 4% by mass.
• % range is suitable from the viewpoint of stability during production and improvement of water resistance, weather resistance, etc. of the resulting coating film.
• the shell portion of copolymer (II) preferably contains a carboxyl group-containing monomer as the polymerizable unsaturated monomer (a3).
• Acrylic acid and/or methacrylic acid is particularly suitable as the carboxyl group-containing monomer.
• the amount of the carboxyl group-containing monomer is preferably 1 based on the total mass of the plurality of polymerizable unsaturated monomers (a3) from the viewpoint of stability of the emulsion resin in an aqueous medium, water resistance of the resulting coating film, etc.
• a range of from 1 to 40% by mass, more preferably from 6 to 25% by mass, and even more preferably from 7 to 19% by mass is suitable from the viewpoint of improving storage stability and water resistance of the resulting coating film.
• the plurality of polymerizable unsaturated monomers (a3) forming the shell portion of the copolymer (II) are selected as at least a part of the components thereof. It is suitable to contain the above-mentioned hydroxyl group-containing monomer in order to improve the stability of the emulsion resin in an aqueous medium.
• the hydroxyl group-containing monomer 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate are particularly suitable. .
• the amount of the hydroxyl group-containing monomer is generally determined based on the total mass of the plurality of polymerizable unsaturated monomers (a3) from the viewpoint of the stability of the emulsion resin in an aqueous medium and the water resistance of the resulting coating film.
• a range of 1 to 40% by weight, preferably 3 to 25% by weight, and more preferably 4 to 20% by weight is suitable from the viewpoint of storage stability and improved water resistance of the resulting coating film.
• the core-shell emulsion is produced by, for example, emulsion polymerizing a monomer mixture (1) containing a polymerizable unsaturated monomer (a1) and a polymerizable unsaturated monomer (a2) in the above ratio to produce a copolymer (I), and then It can be obtained by adding a monomer mixture (2) containing a plurality of polymerizable unsaturated monomers (a3) and further emulsion polymerization.
• Emulsion polymerization of the monomer mixture (1) can be carried out by a method known per se, for example, by using a polymerization initiator in the presence of an emulsifier.
• the monomer mixture (2) may optionally contain components such as a polymerization initiator, a chain transfer agent, a reducing agent, and an emulsifier.
• the core-shell emulsion has a core of a copolymer (I) formed from a monomer mixture (1) containing a polymerizable unsaturated monomer (a1) and a polymerizable unsaturated monomer (a2), and contains a plurality of polymerizable unsaturated monomers. It is a core/shell type emulsion whose shell is a copolymer (II) formed from a monomer mixture (2) containing (a3).
• the ratio of copolymer (I) to copolymer (II) is generally 5 as the solid content mass ratio of copolymer (I)/copolymer (II) from the viewpoint of sagging resistance of the resulting coating film. It is preferably within the range of /95 to 95/5, particularly 30/70 to 92/8, and even more particularly 40/60 to 90/10.
• the acrylic resin emulsion (A) a single-layer acrylic resin emulsion obtained by one-stage emulsion polymerization can also be used.
• the acrylic resin emulsion (A) obtained as described above is preferably 5 to 90 mgKOH/g, more preferably 8 to 60 mgKOH/g, and even more preferably 10 It has a resin acid value in the range of ⁇ 50 mg KOH/g.
• the acrylic resin emulsion (A) is preferably in the range of 1 to 100 mgKOH/g, more preferably 2 to 90 mgKOH/g, and still more preferably 5 to 80 mgKOH/g, from the viewpoint of water resistance of the resulting coating film.
• the resin has a hydroxyl value of
• the content of the acrylic resin emulsion (A) is 15 to 60% by mass based on the resin solid content in the aqueous colored coating composition. %, more preferably 20 to 55% by weight, even more preferably 25 to 45% by weight.
• the above water-based colored coating composition can further include a curing agent.
• the curing agent include amino resins, polyisocyanate compounds, blocked polyisocyanate compounds, epoxy group-containing compounds, carboxyl group-containing compounds, carbodiimide group-containing compounds, hydrazide group-containing compounds, semicarbazide group-containing compounds, and the like.
• preferred are amino resins, polyisocyanate compounds and blocked polyisocyanate compounds that can react with hydroxyl groups, and carbodiimide group-containing compounds that can react with carboxyl groups.
• the aqueous colored coating composition further contains a viscosity modifier (B).
• a viscosity modifier B
• polyacrylic acid-based viscosity modifier silica-based fine powder, mineral-based viscosity modifier, barium sulfate micronized powder, polyamide-based viscosity modifier, organic resin fine particle viscosity modifier, diurea-based viscosity modifier Modifiers, urethane-associated viscosity modifiers, cellulose-based viscosity modifiers, etc. are mentioned, and polyacrylic acid-based viscosity modifiers are preferred.
• the content of the viscosity modifier (B) is 0.0000000000000000 based on the resin solid content in the water-based colored paint composition. It is preferably within the range of 1 to 10% by mass, more preferably within the range of 0.5 to 8% by mass, and even more preferably within the range of 1.0 to 6.0% by mass.
• the above water-based colored paint composition may contain colored pigments, bright pigments, dyes, thickeners, curing catalysts, ultraviolet absorbers, light stabilizers, antifoaming agents, plasticizers, surface conditioners, anti-settling agents, as necessary. It can contain various paint additives such as additives.
• the multilayer coating film forming method of the present disclosure includes the following steps. ⁇ Step 1: By discharging a predetermined water-based colored paint composition close to the object to be coated using a liquid discharge head that controls discharge by changing the relative distance between the valve body and the discharge port, the above-mentioned Step of forming a colored coating film on the object to be coated/Step 2: Step of coating the above colored coating film with a clear coating composition to form a clear coating film.
• the liquid ejection head that controls ejection by changing the relative distance between the valve body and the ejection port is as described in the section of "Aqueous colored paint composition".
• the dry film thickness of the colored coating film formed from the water-based colored coating composition varies depending on the use of the object to be coated and is not particularly limited, but is preferably 1.0 to 15.0 ⁇ m, more preferably 3.0 to 15.0 ⁇ m. .0 ⁇ m, and more preferably 5.0 to 15.0 ⁇ m. This is from the viewpoint of the clarity of the multilayer coating film.
• the objects to be coated include, for example, the outer panels of automobile bodies such as passenger cars, trucks, motorcycles, and buses; automobile parts; and the outer panels of household electrical appliances such as mobile phones and audio equipment; External panels and automobile parts are preferred.
• the material to be coated is not particularly limited, and examples include iron, aluminum, brass, copper, tinplate, stainless steel, galvanized steel, zinc alloys (Zn-Al, Zn-Ni, Zn-Fe), etc. etc.)
• Metal materials such as plated steel; resins such as polyethylene resin, polypropylene resin, acrylonitrile-butadiene-styrene (ABS) resin, polyamide resin, acrylic resin, vinylidene chloride resin, polycarbonate resin, polyurethane resin, epoxy resin, etc.
• resins such as polyethylene resin, polypropylene resin, acrylonitrile-butadiene-styrene (ABS) resin, polyamide resin, acrylic resin, vinylidene chloride resin, polycarbonate resin, polyurethane resin, epoxy resin, etc.
• plastic materials such as fiber reinforced plastic (FRP); inorganic materials such as glass, cement, and concrete; wood; fibrous materials such as paper and cloth.
• the surfaces of the above-mentioned objects to be coated include phosphate treatment, chromate treatment, composite oxide treatment, etc. It may be one that has been subjected to surface treatment such as treatment.
• a coating film may be further formed on the object, which may or may not be surface-treated.
• the substrate to be coated may be surface-treated as necessary, and an undercoat film may be formed thereon, or an intermediate coat film may be formed on the undercoat film.
• the above-mentioned undercoat film and intermediate coating film can be formed using known undercoat and intermediate coating paints that are commonly used in the painting of automobile bodies. can.
• the above-mentioned close ejection is not particularly limited as long as the distance between the ejection port and the object to be coated is such that the liquid ejection head described above is generally used, and is preferably 0.1 to 50.0 mm, more preferably 0. .5 to 30 mm, and more preferably 1.0 to 10.0 mm.
• the frequency at which the aqueous colored paint composition is discharged from the valve body is 10 to 10,000 Hz from the viewpoint of discharge stability and the difficulty of causing unevenness in the formed coating film. It is preferably within the range of , more preferably within the range of 30 to 5,000 Hz, and even more preferably within the range of 50 to 3,000 Hz.
• the supply pressure for supplying the aqueous colored coating composition to the liquid ejection head is preferably within the range of 0.001 to 10 MPa, and 0.005 MPa from the viewpoint of supply stability. It is more preferably within the range of ⁇ 5.0 MPa, and even more preferably within the range of 0.01 ⁇ 1.0 MPa.
• the scanning speed of the liquid ejection head should be within the range of 10 to 1,500 mm/s from the viewpoint of ejection stability and resistance to unevenness of the formed coating film. The speed is preferably within the range of 50 to 1,000 mm/s, and even more preferably within the range of 100 to 800 mm/s.
• the pitch at which the liquid ejection head scans is preferably within the range of 0.001 to 1.0 mm, preferably 0.005 to 1.0 mm, from the viewpoint of coating efficiency, etc. It is more preferably within the range of 0.01 to 1.0 mm, and even more preferably within the range of 0.01 to 1.0 mm.
• Examples of the clear paint composition include curable clear paint compositions (for example, thermosetting clear paint compositions, photocurable clear paint compositions), and non-curable clear paint compositions.
• examples of the thermosetting clear coating composition include organic solvent-based thermosetting coating compositions containing a base resin having a crosslinkable functional group and a curing agent, water-based thermosetting coating compositions, and powder thermosetting coating compositions. Examples include paint compositions and the like.
• Examples of the crosslinkable functional groups that the base resin has include carboxyl groups, hydroxyl groups, epoxy groups, and silanol groups.
• Examples of the base resin include acrylic resin, polyester resin, alkyd resin, urethane resin, epoxy resin, and fluororesin.
• Examples of the curing agent include polyisocyanate compounds, blocked polyisocyanate compounds, melamine resins, urea resins, carboxyl group-containing compounds, carboxyl group-containing resins, epoxy group-containing resins, and epoxy group-containing compounds.
• the base resin/curing agent combinations of the above clear coating composition include hydroxyl group-containing resin/polyisocyanate compound, carboxyl group-containing resin/epoxy group-containing resin, hydroxyl group-containing resin/blocked polyisocyanate compound, hydroxyl group-containing resin/melamine resin. etc. are preferred, and hydroxyl group-containing resin/polyisocyanate compound is more preferred.
• the clear paint composition may be a one-component paint or a multi-component paint such as a two-component urethane resin paint.
• the above-mentioned clear paint composition may contain coloring pigments, bright pigments, dyes, etc., if necessary, to an extent that does not impede transparency, and may further contain extender pigments, ultraviolet absorbers, light stabilizers, Antifoaming agents, thickeners, rust preventives, surface conditioners, etc. can be included as appropriate.
• the method of applying the clear paint composition is not particularly limited, but a wet coating film can be formed by, for example, air spray painting, airless spray painting, rotary atomization painting, curtain coating, or the like. In these coating methods, electrostatic charge may be applied if necessary. Among these, air spray coating or rotary atomization coating is particularly preferred.
• the amount of the clear coating composition applied is usually such that the cured film thickness is 10 to 70 ⁇ m, preferably 20 to 50 ⁇ m.
• the remaining monomer emulsion (1) was dropped into the reaction vessel maintained at the same temperature over 3 hours, and aged for 1 hour after the dropwise addition was completed. Thereafter, the following monomer emulsion (2) was added dropwise over 1 hour, and after aging for 1 hour, 40 parts of a 5% dimethylethanolamine aqueous solution was gradually added to the reaction vessel while cooling to 30°C. The mixture was discharged while being filtered through a cloth to obtain an acrylic resin emulsion (A1) with a solid content concentration of 30%.
• the obtained acrylic resin emulsion (A1) had an acid value of 33 mgKOH/g and a hydroxyl value of 25 mgKOH/g.
• Monomer emulsion (1) 42 parts of deionized water, 0.72 parts of "Aqualon KH-10", 2.1 parts of methylenebisacrylamide, 2.8 parts of styrene, 16.1 parts of methyl methacrylate, 28 parts of ethyl acrylate, and 21 parts of n-butyl acrylate were mixed and stirred to obtain a monomer emulsion (1).
• Monomer emulsion (2) 18 parts of deionized water, 0.31 parts of "Aqualon KH-10", 0.03 parts of ammonium persulfate, 5.1 parts of methacrylic acid, 5.1 parts of 2-hydroxyethyl acrylate, 3 parts of styrene. 1 part, 6 parts of methyl methacrylate, 1.8 parts of ethyl acrylate, and 9 parts of n-butyl acrylate were mixed and stirred to obtain a monomer emulsion (2).
• the remaining monomer emulsion (3) was added dropwise over 3 hours into a reaction vessel maintained at the same temperature, and aged for 1 hour after completion of the addition.
• the following monomer emulsion (4) was added dropwise over 1 hour, and after aging for 1 hour, 40 parts of a 5% dimethylethanolamine aqueous solution was gradually added to the reaction vessel while cooling to 30°C.
• the mixture was discharged while being filtered through a cloth to obtain an acrylic resin emulsion (A2) with a solid content concentration of 30%.
• the obtained acrylic resin emulsion (A2) had an acid value of 13 mgKOH/g and a hydroxyl value of 65 mgKOH/g.
• Monomer emulsion (3) 46.2 parts of deionized water, 0.79 parts of "Aqualon KH-10", 7.7 parts of styrene, 16.94 parts of methyl methacrylate, 7.7 parts of n-butyl acrylate, n- 30.8 parts of butyl methacrylate, 11.55 parts of 2-hydroxyethyl methacrylate, and 2.31 parts of ethylene glycol dimethacrylate were mixed and stirred to obtain a monomer emulsion (3).
• Monomer emulsion (4) 13.8 parts of deionized water, 0.24 parts of "Aqualon KH-10", 0.03 parts of ammonium persulfate, 2.3 parts of styrene, 6.9 parts of methyl methacrylate, 4. 6 parts of n-butyl acrylate, 3.45 parts of 2-hydroxyethyl methacrylate, and 2.07 parts of methacrylic acid were mixed and stirred to obtain a monomer emulsion (4).
• hydroxyl group-containing acrylic resin (C1) had an acid value of 47 mgKOH/g, a hydroxyl value of 72 mgKOH/g, and a weight average molecular weight of 58,000.
• the pH-adjusted mixed solution was put into a wide-mouthed glass bottle, glass beads with a diameter of about 1.3 mm ⁇ were added as a dispersion medium, the bottle was sealed, and the mixture was dispersed in a paint shaker for 4 hours to obtain a pigment dispersion (P-1). I got it.
• the pH-adjusted mixed solution was put into a wide-mouthed glass bottle, glass beads with a diameter of about 1.3 mm ⁇ were added as a dispersion medium, the bottle was sealed, and the mixture was dispersed in a paint shaker for 4 hours to obtain a pigment dispersion (P-2). I got it.
• the pH-adjusted mixed solution was placed in a wide-mouthed glass bottle, glass beads with a diameter of about 1.3 mm ⁇ were added as a dispersion medium, the bottle was sealed, and the mixture was dispersed for 4 hours in a paint shaker to form a pigment dispersion (P-3). I got it.
• the pH-adjusted mixed solution was put into a wide-mouthed glass bottle, glass beads with a diameter of about 1.3 mm ⁇ were added as a dispersion medium, the bottle was sealed, and the mixture was dispersed in a paint shaker for 4 hours to obtain a pigment dispersion (P-4). I got it.
• Example 1 water-based colored coating composition No. 1 was prepared in the same manner as in Example 1, except that the composition was as shown in Table 1 below. 2 ⁇ No. I got 24. In addition, the numerical values shown in Table 1 mean solid content.
• tan ⁇ At a temperature of 23°C, the shear stress was 1.0 Pa, the frequency was 0.1 Hz, and the tan ⁇ (loss modulus/storage modulus) at the temperature of 23°C was determined by "HAAKE RheoStress RS150" (trade name, manufactured by HAAKE, diameter 35 mm). , 2° inclined cone and plate).
• V 3 viscosity after holding the sample for 50 seconds at a shear rate of 0.1 sec -1 was measured. Subsequently, the shear rate was changed to 1000 sec -1 and the viscosity (V 4 ) was measured after holding for 10 seconds. Subsequently, the shear rate was changed to 0.1 sec -1 and the viscosity (V5) was measured after holding for 10 seconds. All measurements were performed at a temperature of 23° C. using “HAAKE RheoStress RS150” (trade name, manufactured by HAAKE, cone and plate with a diameter of 35 mm and a 2° inclination).
• ⁇ There is no distortion in the linear object. ⁇ : There is some distortion in the linear object, but there is no practical problem. ⁇ : The linear object is distorted as a whole, and there is a problem in practical use. ⁇ : Unable to form a linear object.
• the coating was applied with a film thickness gradient so as to obtain a film thickness of approximately 10 ⁇ m to 40 ⁇ m in the direction, and the coated plate was stood approximately vertically and allowed to stand for 3 minutes, followed by preheating at 80° C. for 3 minutes. Next, after being left for 7 minutes, the coating was heated at 140° C. for 30 minutes to harden the coating film, thereby producing a coated plate for sagging resistance testing.
• the film thickness at the position of the punch hole where the film thickness is the thinnest among the punch holes where 5 mm or more of paint film sag is observed from the lower end of the punch hole [sagging limit] Film thickness ( ⁇ m)] was measured and evaluated. The larger the sagging limit film thickness, the better the sagging resistance. ⁇ and ⁇ are passed. The evaluation results are shown in Table 1.
• the sag limit film thickness is 15 ⁇ m or more and less than 20 ⁇ m.
• the sag limit film thickness is 10 ⁇ m or more and less than 15 ⁇ m.
• the sag limit film thickness is less than 10 ⁇ m.
• [Preparation of coated object for sharpness test] [Preparation of coated object (O-1) for sharpness test] The surface of a black polypropylene plate measuring 100 mm long x 100 mm wide x 2 mm thick was wiped with gauze soaked in petroleum benzine to degrease it, and then "Ascalex #2850" (trade name, manufactured by Kansai Paint Co., Ltd., A polyolefin-containing water-based primer paint) was applied with a hand spray gun to a cured film of 15 ⁇ m, left for 5 minutes, and then preheated at 80°C for 3 minutes. )It was created.
• Ascalex #2850 trade name, manufactured by Kansai Paint Co., Ltd., A polyolefin-containing water-based primer paint
• Example 21 [Preparation of painted plate for sharpness test] [Preparation of painted plate for sharpness test (S1)] Water-based colored paint composition No. 1 was filled into "X JET” (trade name, manufactured by SSI JAPAN, high viscosity minute piezo jet dispenser, discharge opening diameter 100 ⁇ m), and applied to the object to be coated for image clarity test (O-1) at a frequency of 350 Hz and a supply pressure of 350 Hz. 0.03 MPa, a distance of 10 mm between the discharge port and the object to be coated, 27°C, and 50% relative humidity, the coating was applied to a dry film thickness of 10 ⁇ m, left at room temperature for 5 minutes, and then heated to 80°C for 30 minutes.
• X JET trade name, manufactured by SSI JAPAN, high viscosity minute piezo jet dispenser, discharge opening diameter 100 ⁇ m
• An uncured colored coating film was formed by preheating for a minute.
• the clear coating composition (Z-1) obtained in Production Example 9 was applied to the uncured colored coating film using a hand spray gun so that the cured film thickness was 35 ⁇ m, and after being left for 7 minutes, it was heated at 120°C.
• a coated plate for sharpness test (S1-1) was prepared by heating for 30 minutes to cure the colored coating film and clear coating film.
• Example 21 coated plates for sharpness test (S1-2) to (S1- 28), (S2-2) to (S2-28), (S3-2) to (S3-28), (S4-2) to (S4-28) and (S5-2) to (S5-28) was created.
• SW Short Wave
• Wave Scan trade name, manufactured by BYK Gardner

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