WO2006054611A1 - Materiau de revetement en couleur a base d'eau, dispersion aqueuse de resine de melamine hydrophobe et procede de production correspondant, composition de revetement a base d'eau, et procede de formation de film multicouche - Google Patents

Materiau de revetement en couleur a base d'eau, dispersion aqueuse de resine de melamine hydrophobe et procede de production correspondant, composition de revetement a base d'eau, et procede de formation de film multicouche Download PDF

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Publication number
WO2006054611A1
WO2006054611A1 PCT/JP2005/021056 JP2005021056W WO2006054611A1 WO 2006054611 A1 WO2006054611 A1 WO 2006054611A1 JP 2005021056 W JP2005021056 W JP 2005021056W WO 2006054611 A1 WO2006054611 A1 WO 2006054611A1
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WIPO (PCT)
Prior art keywords
water
parts
paint
coating film
resin
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PCT/JP2005/021056
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English (en)
Japanese (ja)
Inventor
Kouki Hayashi
Shinya Yamada
Kouichi Ohara
Hiroto Yoneda
Tomohito Asai
Shinya Furuta
Hiroki Ando
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Nippon Paint Co., Ltd.
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Application filed by Nippon Paint Co., Ltd. filed Critical Nippon Paint Co., Ltd.
Priority to JP2006545104A priority Critical patent/JP5048337B2/ja
Publication of WO2006054611A1 publication Critical patent/WO2006054611A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08L61/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
    • C08L61/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine
    • 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
    • B05D7/532—Base coat plus clear coat type the two layers being cured or baked together, i.e. wet on wet
    • 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
    • B05D2401/00—Form of the coating product, e.g. solution, water dispersion, powders or the like
    • B05D2401/20—Aqueous dispersion or solution
    • 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
    • B05D2502/00—Acrylic polymers

Definitions

  • the present invention relates to an aqueous coloring paint, a hydrophobic melamine rosin water dispersion and a method for producing the same, an aqueous coating composition, and a method for forming a multilayer coating film.
  • a resin composition containing a resin such as an acrylic resin having a functional group such as a carboxyl group and a hydroxyl group and a melamine resin as a crosslinking agent is used as an electrodeposition coating, an intermediate coating, Widely used for applications such as water-based paints used for top coats (including base paints and top coats). It has been proposed to use hydrophobic melamine resin as a crosslinking agent for such water-based paints.
  • Patent Document 5 includes an acrylic resin (A), a hydrophobic melamine resin (B), and a polyester resin (C) having a weight average molecular weight of 5000 to 100000, an acid value of 10 to LOOmgKOHZg, and a hydroxyl value of 20 to 200.
  • An aqueous rosin dispersion is disclosed which comprises a reaction product obtained by warming and having a thickening rate of 20 to 200% before and after the warming. This is intended to improve performance such as water dispersibility by modifying hydrophobic melamine resin using high acid value acrylic resin.
  • Patent Document 1 Japanese Patent Laid-Open No. 52-107029
  • Patent Document 2 JP-A-52-103426
  • Patent Document 3 JP-A-53-99232
  • Patent Document 4 Japanese Patent Application Laid-Open No. 54-16540
  • Patent Document 5 Japanese Patent Application Laid-Open No. 2002-308993
  • the present invention provides a hydrophobic melamine rosin water dispersion capable of obtaining a coating film having excellent storage stability and excellent adhesion and surface smoothness. It is an object of the present invention to provide a water-based coloring paint, a water-based paint composition, and a multilayer coating film forming method capable of obtaining a coating method having excellent color forming property, recoat adhesion, chipping property, and water-resistant adhesion property. To do.
  • the present invention is an aqueous colored paint containing a film-forming resin, a curing agent and a pigment, wherein the film-forming resin has an acid value of 1 to 30 mg KOHZg and a hydroxyl value of 10 to 150.
  • a water-based colored paint comprising acrylic resin emulsion produced by polymerization, wherein the curing agent contains a hydrophobic melamine resin aqueous dispersion having a particle size of 20 to 140 nm.
  • the hydrophobic melamine rosin water dispersion comprises an acrylic resin having an acid value of 105 to 200 mg KOHZg, a hydroxyl value of 100 to 200, and a number average molecular weight of 1000 to 5,000, and a hydrophobic melamine resin having 5Z9 5 to 50Z50. It is preferably obtained by a production method including a step (1) of mixing and heating at a mass ratio and a step (2) of dispersing the heated product obtained in the above step (1) in water.
  • the hydrophobic melamine greaves preferably have a solubility parameter (SP) in the range of 9.0 ⁇ SP ⁇ 11.5.
  • SP solubility parameter
  • the acrylic resin emulsion has a particle size of 20 to 140 nm!
  • the acrylic resin emulsion is preferably obtained by two-stage emulsion polymerization.
  • the acrylic resin emulsion obtained by the second-stage emulsion polymerization preferably has an acid value of 25 to 200 mgKOHZg.
  • the present invention also includes a step (I) of applying a water-based base paint on an object to be coated to form a base paint film, and applying a clear paint on the base paint film without curing. And forming a clear single coating film (ii) and a step (III) of simultaneously heating the base coating film and the clear single coating film, wherein the water-based base coating material is used.
  • a method for forming a multilayer coating film characterized by being the above-mentioned water-based colored paint.
  • the object to be coated is preferably subjected to a chemical conversion treatment to form an electrodeposition coating film and an intermediate coating film.
  • the present invention is also a multilayer coating film formed by the above-described multilayer coating film forming method.
  • the present invention also provides an attalinole tree essence having an acid value of 105 to 200 mg KOHZg, a hydroxyl value of 100 to 200, and a number average molecular weight of 1000 to 5000, and a hydrophobic 'melamine tree essence of 5/95 to 50/50.
  • a method for producing a hydrophobic melamine rosin water dispersion characterized by comprising.
  • the hydrophobic melamine resin preferably has a solubility parameter (SP) in the range of 9.0 ⁇ SP ⁇ 11.5. .
  • the present invention is also a hydrophobic melamine resin aqueous dispersion obtained by the above-described method for producing a hydrophobic melamine resin aqueous dispersion.
  • the present invention is also an aqueous coating composition containing a film-forming rosin and a curing agent, wherein the curing agent includes the hydrophobic melamine rosin aqueous dispersion described above. It is also a composition.
  • the coating film-forming resin is obtained by emulsion polymerization of a monomer mixture containing 65% by mass or more of (meth) acrylic acid ester having 1 or 2 carbon atoms in the ester part. It is preferable that it contains the acrylic rosin emulsion obtained.
  • the water-based colored paint of the present invention contains a film-forming resin, a curing agent, and a pigment, and the above-mentioned film-forming resin is an emulsion polymerization having an acid value of 1 to 30 mg KOHZg and a hydroxyl value of 10 to 150.
  • the acrylic resin resin emulsion to be produced is included, and the curing agent includes a hydrophobic melamine resin aqueous dispersion having a particle size of 20 to 140 nm.
  • the coating film which has can be obtained. For this reason, the obtained coating film has little white blurring feeling.
  • the water-based colored paint contains, for example, a blue pigment, a bluish sensation is strong, and when it contains a black pigment, a paint film with a jet black feeling can be obtained.
  • a multilayer coating film in automobile painting when the water-based colored paint is used as a water-based paint, the hydrophobic melamine soot having a particle size of 20 to 140 nm is used together with the acrylic resin emulsion. Since it is formed using a paint containing an oily water dispersion, a multilayer coating film excellent in recoat adhesion, chipping resistance, and water adhesion resistance can be obtained. In addition, a coating film having excellent color development can be obtained. For this reason, in the method for forming a multilayer coating film in automobile painting, the above-mentioned aqueous colored paint can be suitably used as an aqueous base paint.
  • the curing agent contains a hydrophobic melamine rosin water dispersion having a particle size of 20 to 140 nm. Since such a hydrophobic melamine rosin water dispersion is used, a coating film having excellent color developability can be obtained. In addition, when a hydrophobic melamine resin aqueous dispersion is used as a curing agent in the aqueous base coating material in the multilayer coating film forming method, a multilayer coating film having excellent recoat adhesion, chipping resistance, and water adhesion resistance is obtained. Obtainable. If it is less than 20 nm, a significant decrease in the solid content of the paint occurs.
  • the water dispersibility is lowered, and the adhesion and surface smoothness of the formed coating film may be lowered. It is preferably 30 to 120 nm. 50 to: More preferably LOOnm.
  • the particle diameters of the hydrophobic melamine rosin dispersion and acrylic resin emulsion used in the present invention were determined by using ELS-800 (manufactured by Otsuka Electronics Co., Ltd.) and the average dispersed particle diameter value measured under the following conditions. It is. Sample; infinite dilution with ion-exchanged water
  • the above-mentioned hydrophobic melamine resin aqueous dispersion is composed of an acrylic resin having an acid value of 105 to 200 mgKOHZg, a hydroxyl value of 100 to 200, and a number average molecular weight of 1000 to 5000, and a hydrophobic melamine resin in a mass ratio of 5Z9 5 to 50Z50. It is preferably obtained by a production method including the step (1) of mixing and heating and the step (2) of dispersing the heated product obtained in the above step (1) with water. As a result, color development, recoat adhesion, chipping resistance, and water adhesion resistance can be improved. A method for producing such a hydrophobic melamine rosin aqueous dispersion is also one aspect of the present invention.
  • an attalinole tree essence having an acid value of 105 to 200 mg KOHZg, a hydroxyl value of 100 to 200, and a number average molecular weight of 1000 to 5000 and a hydrophobic 'melamine tree essence are 5/95 to 50/50.
  • a step of mixing and heating at a mass ratio is performed [step (1)]. By performing the step (1), a heating product of the acrylic resin and the hydrophobic melamine resin can be obtained.
  • the acrylic resin has an acid value of 105 to 200 mg KOHZg. If it is less than 105 mg KOHZg, the particle size may exceed 140 nm. Exceeding 200mgKOHZg may give gel during heating. It is preferably 105 to 180 mg KOHZg.
  • the acrylic resin has a hydroxyl value of 100 to 200. If it is less than 100, the particle size may exceed 140 nm. If it exceeds 200, reaction control may become extremely difficult. It is preferable that it is 120-180.
  • the acid value of the said acrylic resin is a measured value, and a hydroxyl value is a calculated value.
  • the acrylic resin has a number average molecular weight of 1,000 to 5,000. If it is less than 1000, the particle size may exceed 140 nm. If it exceeds 5000, there is a risk of giving gel during heating S. It is preferable that it is 1500-4000!
  • the number average molecular weight of the acrylic resin is measured under the following GPC system measurement conditions. Value.
  • TSK STANDARD POLYSTYRENE manufactured by Tosoh Corporation
  • the acrylic resin includes, for example, a carboxylic acid group-containing unsaturated monomer, a hydroxyl group-containing unsaturated monomer, and, if necessary, other ⁇ , ⁇ -ethylenically unsaturated monomers and wrinkles or crosslinks in a water-soluble organic solvent.
  • a monomer composition containing a reactive monomer can be obtained using a known polymerization method such as solution polymerization.
  • the carboxylic acid group-containing unsaturated monomer is not particularly limited, and examples thereof include acrylic acid, methacrylic acid, acrylic acid dimer, crotonic acid, 2-atallylooxychetyl phthalic acid, and 2 taliloylo.
  • hydroxyl group-containing unsaturated monomer examples include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, aryl alcohol, methacrylic alcohol, and (meth) acrylic.
  • ⁇ -force prolatatatone adduct of hydroxyethyl ester can be mentioned.
  • Examples of the other ⁇ , ⁇ ethylenically unsaturated monomers include, for example, carbon in the ester portion.
  • (meth) acrylic acid ester having 3 or more carbon atoms in the ester moiety [for example, (meth) acrylic acid N-Butyl acid, Isobutyl (meth) acrylate, t-Butyl (meth) acrylate, (Meth) acrylic acid 2-ethylhexyl, lauryl methacrylate, acrylic acid phenol, (meth) acrylic acid isoborn , Cyclohexyl methacrylate, t-butylcyclohexyl (meth) acrylate, dicyclopentagel (meth) acrylate, dihydrodicyclopentagenyl (meth) acrylate, stearyl methacrylate
  • the unsaturated monomer having two or more unsaturated double bonds is not particularly limited as long as it is a vinyl monomer having two or more radically polymerizable unsaturated groups in the molecule.
  • a bur compound such as dibutylbenzene or divinylsulfone; (meth) aryl (meth) acrylate (hereinafter, both allyl and methallyl are represented by (meth) aryl) and diaryl.
  • (meth) aryl compounds such as dimethallyl phthalate, di (meth) aryl (meth) acrylamide, tri (meth) allyl cyanurate or isocyanurate, tri (meth) aryl trimellitate, bis ((meth) aryl nadiimide) Mono or polyethylene glycol di ( Mono- or polyoxyalkylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol di (meth) acrylate, penta such as (meth) acrylate, mono or polypropylene glycol di (meth) acrylate Examples include (meth) atari toy compounds such as erythritol tri (meth) acrylate and glycerol tri (meth) acrylate.
  • aryloxypolyethylene glycol polypropylene glycol monoacrylate (Blemmer AKEP manufactured by NOF Corporation), dicyclomentenyl acrylate (F ANCRYL FA-511A manufactured by Hitachi Chemical Co., Ltd.), dicyclomenthe-loxochetyl acrylate (Hitachi Chemical) FA NCRYL FA-512A), dicyclomenthyl oxychetyl metatalylate (FA KCRYL FA-512M manufactured by Hitachi Chemical Co., Ltd.), dihydrodicyclopentagel talate (commercially available from BASF), 3 —Cyclohexylmethyl metatalylate (commercially available from Daicel), 3-cyclohexylmethyl atallylate (commercially available from Daicel), butanediol 1,4 dibutyl ether (from BASF) And triallyl isocyanurate (TAIC manufactured by Nippon Kasei Co., Ltd.) are commercially available.
  • aryl methacrylate or ethylene glycol di (meth) acrylate is preferable. Particularly preferably, it is an unsaturated monomer having two or more unsaturated double bonds of 4 atoms or less, preferably 3 atoms or less, when the distance between the unsaturated double bonds is expressed by the number of atoms. Specific examples include aryl methacrylate.
  • the unsaturated monomers having two or more unsaturated double bonds can be used alone or in combination of two or more.
  • the solubility parameter ⁇ is preferably in the range of 9.0 ⁇ SP ⁇ 11.5. If it is 9.0 or less, the particle size may exceed 140 nm. 11. If it is 5 or more, the particle size exceeds 140 nm and the performance may be degraded. More preferably, 5 ⁇ SP ⁇ 11.0.
  • the solubility parameter ⁇ is generally called SP (Solubility 'parameter 1) among those skilled in the art, and is a measure indicating the degree of hydrophilicity or hydrophobicity of greaves. It is also an important measure for judging the compatibility between fats.
  • the solubility parameter can be numerically determined based on, for example, a turbidity measurement method (reference: KW Suh , DH Clarke J. Polymer. Sci., A—1, 5, 1671 (1967) .;).
  • the solubility parameter ⁇ in the present specification is a parameter determined by a turbidity measurement method.
  • the solubility parameter according to the turbidity measurement method is, for example, by dissolving a solid matter (predetermined mass) of a resin to be measured in a certain amount of a good solvent (such as acetone), and then adding a poor solvent such as water or hexane.
  • a good solvent such as acetone
  • a poor solvent such as water or hexane
  • the mixing ratio of the acrylic resin to the hydrophobic melamine resin is 5 to 95 to 50 (mass ratio, acrylic resin to hydrophobic melamine resin). I prefer it. If the amount of acrylic resin is less than 5/95, the particle size may exceed 140 nm. If the amount of acrylic resin is greater than 50Z50, the NV (solid content concentration) of the paint may be significantly reduced and reaction control may be extremely difficult. More preferably, it is 10 Z90-40Z60.
  • the mixing method of acrylic resin and hydrophobic melamine resin can be performed by a conventionally known method.
  • the resulting hydrophobic melamine resin aqueous dispersion is used as a curing agent.
  • the function as a curing agent is less likely to deteriorate.
  • the particle size after water dispersion is 20 to 140 nm.
  • the hydrophobic melamine rosin aqueous dispersion obtained by the present invention can be suitably used as a curing agent for water-based colored paints.
  • other resins such as polyester resin may be included within the range not excluding the effect of the present invention.
  • the mixing condition of the acrylic resin and the hydrophobic melamine resin is preferably 75 to 90 ° C with a heating temperature of 70 to 100 ° C. Is more preferred.
  • the heating time is preferably 1 to 10 hours, more preferably 1 to 5 hours. If it is less than the lower limit, the particle size may exceed 140 nm. Exceeding the upper limit may give a gel.
  • the method for producing the hydrophobic melamine rosin aqueous dispersion is carried out by performing step (1) above.
  • a step of obtaining a hydrophobic melamine resin aqueous dispersion having a particle size of 20 to 140 nm is carried out by dispersing the resulting heated product in water [step (2)].
  • step (2) an aqueous dispersion (aqueous dispersion) in which rosin particles having a particle diameter of 20 to 140 nm are dispersed in water can be obtained.
  • the method for water-dispersing the heated product obtained in the step (1) is not particularly limited, and a normal water-dispersing method for rosin can be used. It is preferable to disperse in water by cooling the heated product to a temperature of 50 ° C. or lower and then diluting with water. Thereby, a hydrophobic melamine rosin water dispersion having a particle size of 20 to 140 nm can be suitably obtained. If it is not cooled below 50 ° C, it may not be possible to obtain particles with a particle size of 20-140 nm. It is more preferred to disperse in water by cooling to 30-40 ° C and then diluting with water.
  • the pH can be adjusted to 6.5 to 10 by neutralizing with a base as necessary. This is because the stability in this pH region is high.
  • This neutralization is performed by adding a tertiary amine such as dimethylethanolamine or triethylamine to the system before or after mixing and heating the acrylic resin and the hydrophobic melamine resin. Is preferred.
  • a tertiary amine is added, and then the heated product is cooled to a temperature of 50 ° C or lower and diluted with water. It is particularly preferable to disperse in water. Thereby, a hydrophobic melamine rosin water dispersion having a particle size of 20 to 140 nm can be suitably obtained.
  • the hydrophobic melamine resin aqueous dispersion obtained by the above-described production method is prepared by heating the specific acrylic resin and the hydrophobic melamine resin in a water particle size of 20 to 140 nm in water. Are dispersed. For this reason, in addition to the water-based colored paint according to the first aspect of the present invention, it can be suitably used as a curing agent for water-based paint compositions used for electrodeposition paints, intermediate paints, top-coat paints, etc., particularly in automobile painting. it can.
  • a curing agent since it has a function as a curing agent, it can be used in any application as a curing agent (for example, decorative products, molded products such as machines, electrical parts, textiles, paper processing, adhesives, paints, flame retardants, It can also be applied to concrete plasticizers.
  • a hydrophobic melamine rosin aqueous dispersion is also one aspect of the present invention.
  • an aqueous coating composition comprising the hydrophobic melamine rosin water dispersion Is also one aspect of the present invention.
  • the coating film-forming resin contains an acrylic resin emulsion produced by emulsion polymerization having an acid value of 1 to 30 mg KOHZg and a hydroxyl value of 10 to 150.
  • acrylic resin emulsion examples include those obtained by using the carboxylic acid group-containing unsaturated monomer as a raw material and emulsified by one-stage or multi-stage emulsion polymerization described later.
  • An acrylic resin emulsion as a film-forming resin in the water-based colored paint (aqueous base paint) composition of the present invention has a core part and a shell part by two-stage emulsion polymerization, and is a so-called core-shell type.
  • Acrylic rosin emulsion (A) is preferred.
  • the acrylic resin emulsion (A) can be designed with various changes in acid value, hydroxyl group, and Tg, as will be described later, and several types of emulsions with different design values can be used in combination.
  • the acrylic resin emulsion (A) can be used in combination with an acrylic resin emulsion (B) described later.
  • the coating film-forming resin contains a core-shell type acrylic resin emulsion
  • the core part has an carboxylic acid group-containing unsaturated monomer having an acid value of 0 to LOOmgKOHZg. It is preferable that the monomer mixture (a) is obtained by emulsion polymerization. If it exceeds 1 OOmgKOHZg, the water resistance of the resulting coating film may decrease. More preferred to be 0-50 mgKOHZg.
  • the acid value of the core is the acid value of acrylic resin emulsion obtained by the first stage of emulsion polymerization.
  • the shell part is preferably obtained by emulsion polymerization of a monomer mixture (b) containing a carboxylic acid group-containing unsaturated monomer having an acid value of 25 to 200 mg KOH / g. If the acid value is below 25 mg KOHZg, the stability of emulsion may be reduced. If it exceeds 200 mgKOHZg, the water resistance of the resulting coating film may be reduced. 30 to 180 mgKOHZg is preferred.
  • the monomer mixture (a) and Z or the monomer mixture (b) may have a hydroxyl group.
  • the hydroxyl value is 10 to 150, preferably 15 to 120. Up If the hydroxyl value is less than 10, sufficient curability may not be obtained. If it exceeds 150, various performances of the resulting coating film may be deteriorated.
  • the monomer mixture (a) and Z or the monomer mixture (b) may contain a hydroxyl group-containing unsaturated monomer.
  • hydroxyl group-containing unsaturated monomer examples include the hydroxyl group-containing unsaturated monomer described above.
  • the monomer mixture (a) and Z or the monomer mixture (b) may contain a crosslinkable monomer as required.
  • examples of the crosslinkable monomer include the crosslinkable monomers described above.
  • the content of the crosslinkable monomer is preferably 0.05% by mass for the lower limit and 30.0% by mass for the upper limit in 100% by mass of the monomer mixture (a) or the monomer mixture (b). If the amount is less than 0.05% by mass, the resulting multi-layer coating film has problems in color development, and the effect of adding these monomers cannot be obtained. 30. When more than 0 mass 0/0, it may become difficult to synthesize acrylic ⁇ Emma Roussillon.
  • the above content is more preferably a lower limit of 0.5% by mass and an upper limit of 10% by mass.
  • the monomer mixture (a) and Z or the monomer mixture (b) may contain the other a, ⁇ -ethylenically unsaturated monomers.
  • the glass transition temperature (Tg) of the core shell acrylic resin emulsion is preferably 20 to 80 ° C. from the viewpoint of the physical properties of the coating film to be obtained.
  • the monomer mass ratio of the monomer mixture (a) Z monomer mixture (b) [core part Z shell part] is preferably 50Z50 to 98Z2, more preferably 70 to 30 to 5-5. If the shell ratio is larger than 50 to 50, the stability of the emulsion is lowered. If the shell ratio is smaller than 98 to 2, the water resistance of the resulting coating film may be lowered.
  • the Tg of the core-shell type acrylic resin emulsion is a value obtained by calculating the compounding power of various unsaturated monomers in the monomer mixture (a) and the monomer mixture (b).
  • the emulsion polymerization for obtaining the acrylic resin emulsion (A) can be carried out using a generally well-known method.
  • the emulsifier is dissolved in water or an aqueous medium containing an organic solvent such as alcohol as necessary, and the monomer mixture (a) or the monomer mixture (b) and a polymerization initiator are heated and stirred. Can be carried out by dripping. A monomer mixture (a) or a monomer mixture (b) pre-emulsified with an emulsifier and water may be dropped in the same manner! /.
  • Examples of the polymerization initiator include azo oily compounds (for example, azobisisobutyl-tolyl, 2,2'-azobis (2-methylbutyoxy-tolyl), 2,2'-azobis (2,4 dimethyl benzene).
  • azo oily compounds for example, azobisisobutyl-tolyl, 2,2'-azobis (2-methylbutyoxy-tolyl), 2,2'-azobis (2,4 dimethyl benzene).
  • water-based compounds eg, cation-based 4, A′-azobis (4-cyananovaleric acid), cationic 2,2′-azobis (2-methylpropionamidine)
  • Redox oily peroxides for example, benzoyl peroxide, parachlorobenzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, etc.
  • aqueous peroxides for example, potassium persulfate, peroxide) Acid humum etc.
  • Examples of the emulsifiers include those often used by those skilled in the art.
  • reactive emulsifiers such as Antox MS-60 (manufactured by Nippon Emulsifier Co., Ltd.), Eleminol JS-2 (Sanyo Kasei Kogyo Co., Ltd.), Adeka Soap NE-20 (Asahi Denka Co., Ltd.) and Aqualon HS-10 (Daiichi Kogyo Seiyaku Co., Ltd.) are preferred.
  • a mercabtan such as lauryl mercabtan and a chain transfer agent such as ⁇ -methylstyrene dimer may be used as necessary.
  • the reaction temperature is determined by the polymerization initiator. For example, it is preferably 60 to 90 ° C for an azo initiator and 30 to 70 ° C for a redox system. In general, the reaction time is 1 to 8 hours.
  • the content of the polymerization initiator with respect to the total mass of the monomer mixture (a) and the monomer mixture (b) is generally 0.1 to 5% by mass, and preferably 0.2 to 2% by mass. .
  • the particle diameter (A) of the acrylic resin emulsion is preferably in the range of 20 to 140 nm.
  • the adjustment of the particle size is, for example, adjusting the monomer composition and emulsion polymerization conditions. Is possible. More preferably, it is 30 to 120 nm. 50: Power to be LOOnm S More preferable.
  • the said particle diameter is the value measured by the method similar to the particle diameter of the hydrophobic melamine rosin water dispersion mentioned above.
  • the acrylic rosin emulsion (A) is neutralized with a base as necessary to adjust the pH.
  • This neutralization is preferably carried out by adding a tertiary amine such as dimethylethanolamine or triethylamine to the system before or after emulsion polymerization.
  • the acrylic resin emulsion (A) preferably has an acid value of 1 to 30 mg KOHZg. If it is less than lmgKOHZg, the stability of emulsion may be lowered. If it exceeds 3 OmgKOHZg, the water resistance of the resulting coating film may be reduced. Preferred to be 3-25 mg KOHZg.
  • the acrylic resin emulsion (A) has a hydroxyl value of 10 to 150. If it is less than 10, the physical properties of the coating film may be deteriorated. If it exceeds 150, the water resistance of the resulting coating film may decrease. It is preferable that it is 15-120.
  • the acid value of the acrylic resin emulsion is an actual measurement value, and the hydroxyl value is a value obtained by calculating the cohesive strength of various unsaturated monomers used in the synthesis.
  • the content of the acrylic resin emulsion (A) in the water-based colored coating is preferably 5 to 95% by mass, more preferably 10 to 85% by mass in the solid content of the coating. More preferably, it is 20 to 70% by mass. When the content is outside the above range, the coating workability and the appearance of the resulting coating film may be deteriorated.
  • alpha carbon atoms of the ester moiety contains one or two of (meth) acrylic acid ester 65 mass 0/0 above, the ⁇ -ethylenically unsaturated monomer mixture It may contain acrylic resin emulsion obtained from emulsion polymerization.
  • the ⁇ , ⁇ -ethylenically unsaturated monomer mixture preferably has an acid value of 1 to 30 mgKOHZ g, more preferably 3 to 25 mgKOHZg.
  • the ⁇ , ⁇ -ethylenically unsaturated monomer mixture preferably has a hydroxyl value of 10 to 150, more preferably 20 to : L00. If it is less than 10, sufficient curability cannot be obtained, and if it exceeds 150, the water resistance of the coating film may be lowered.
  • the glass transition temperature of the polymer obtained by copolymerizing the above ⁇ , ⁇ ethylenically unsaturated monomer mixture is between 20 and 80 ° C., and the mechanical properties of the resulting coating film are also favorable. Good.
  • the a, j8-ethylenically unsaturated monomer mixture can have the acid value and the hydroxyl value by containing an ⁇ , ⁇ -ethylenically unsaturated monomer having an acid group or a hydroxyl group therein.
  • Examples of the a, ⁇ -ethylenically unsaturated monomer having an acid group include those similar to the carboxylic acid group-containing unsaturated monomer described above. Among these, acrylic acid, methacrylic acid, and acrylic acid dimer are preferable.
  • examples of the ⁇ , ⁇ -ethylenically unsaturated monomer having a hydroxyl group include those similar to the above-mentioned hydroxyl-containing unsaturated monomer. Preferred among these are hydroxyethyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyethyl (meth) acrylate and ⁇ -force prolatatone.
  • the a, j8-ethylenically unsaturated monomer mixture may further contain other ⁇ , ⁇ -ethylenically unsaturated monomers.
  • the other ⁇ , ⁇ ethylenically unsaturated monomers other than the (meth) acrylic acid ester having 1 or 2 carbon atoms in the ester portion among the other a, ⁇ ethylenically unsaturated monomers described above, for example.
  • These can be selected according to the purpose, but (meth) acrylamide is preferably used for easily imparting hydrophilicity.
  • the ⁇ , ⁇ ethylenically unsaturated monomer mixture may contain a crosslinkable monomer.
  • the crosslinkable monomer include those described above.
  • the a, j8 ethylenically unsaturated monomer other than the (meth) acrylic acid ester having 1 or 2 carbon atoms in the ester portion is the a, j8 ethylenically unsaturated monomer.
  • the content in the mixture must be set to less than 35% by weight.
  • the acrylic resin emulsion (B) is obtained by emulsion polymerization of the ex, ⁇ -ethylenically unsaturated monomer mixture.
  • the emulsion polymerization carried out here can be carried out using a generally well-known method. Specifically, the emulsifier is dissolved in water or an aqueous medium containing an organic solvent such as alcohol as necessary, and the ⁇ , ethylenically unsaturated monomer mixture and the polymerization initiator are added dropwise under heating and stirring. Can be done. An ⁇ , ⁇ -ethylenically unsaturated monomer mixture pre-emulsified with an emulsifier and water may be similarly added dropwise.
  • Examples of the polymerization initiator and the emulsifier include those described above.
  • a mercabtan such as lauryl mercabtan and a chain transfer agent such as ⁇ -methylstyrene dimer may be used as necessary.
  • the reaction temperature is determined by the initiator, and for example, it is preferably 60 to 90 ° C for a azo initiator and 30 to 70 ° C for a redox system. In general, the reaction time is 1 to 8 hours.
  • the amount of initiator relative to the total amount of the a, j8-ethylenically unsaturated monomer mixture is generally 0.1-5% by weight, preferably 0.2-2% by weight.
  • the emulsion polymerization can be performed in one stage or in multiple stages, for example, in two stages. That is, first, a part of the ⁇ , ⁇ ethylenically unsaturated monomer mixture ( ⁇ , ⁇ ethylenically unsaturated monomer mixture 1) is emulsion-polymerized, and the ⁇ , ⁇ -ethylene unsaturated monomer mixture The remainder (a, e ethylenically unsaturated monomer mixture 2) is further added to carry out emulsion polymerization. That is, the acrylic resin emulsion (B) may have the structure of the core-shell type emulsion resin.
  • the a, j8-ethylenically unsaturated monomer mixture 1 preferably contains an ⁇ , ⁇ -ethylenically unsaturated monomer having an amide group. At this time, it is further preferable that the a, j8-ethylenically unsaturated monomer mixture 2 does not contain an a, j8-ethylenically unsaturated monomer having an amide group.
  • the particle diameter of the acrylic resin emulsion (B) thus obtained is preferably in the range of 20 to 500 nm, more preferably in the range of 20 to 140 nm. If the particle size is less than 20 ⁇ m, the solid content of the paint may be too low, causing problems in workability. On the other hand, if it exceeds 500 nm, the appearance of the resulting coating film may be deteriorated.
  • the particle size can be adjusted, for example, by adjusting the monomer composition and emulsion polymerization conditions.
  • the acrylic resin emulsion (B) can be used at a pH of 5 to 10 by neutralizing with a base as necessary. This is because the stability in this pH region is high. This neutralization is preferably carried out by adding a tertiary amine such as dimethylethanolamine triethylamine to the system before or after emulsion polymerization.
  • a tertiary amine such as dimethylethanolamine triethylamine
  • Examples of the pigment contained in the water-based colored paint of the present invention include glitter pigments and colored pigments.
  • the shape of the glitter pigment is not particularly limited, and may be colored.
  • the average particle diameter (D) force is 0.05 to 50 ⁇ m and the thickness is 0.1 to 5 ⁇ m.
  • those having an average particle diameter in the range of 10 to 35 / ⁇ ⁇ are excellent in light S and are more preferably used.
  • Specific examples include a non-colored or colored metal brightening agent such as aluminum, copper, zinc, iron, nickel, tin, aluminum oxide, or an alloy, and a mixture thereof. If the bright pigment is a flat pigment, the average particle size (D) is 2 to 50 ⁇ m.
  • any of the above-mentioned bright pigments having an average particle diameter in the range of 10 to 35 / ⁇ ⁇ is excellent in light S and is more preferably used.
  • Other bright pigments include interference pigments, white pigments, graphite pigments and the like.
  • examples of the color pigment include organic azochelate pigments, insoluble azo pigments, condensed azo pigments, phthalocyanine pigments, indigo pigments, perinone pigments, perylene pigments, dioxane pigments, and quinacridone.
  • the total pigment concentration (PWC) in the water-based colored paint is preferably 0.1 to 50%. More preferably ⁇ Also, 0. 5 to 40 0/0, particularly preferably ⁇ or, 1. 0 to 30 0/0. If the upper limit is exceeded, the coating film appearance may be reduced. When a bright pigment is included, the pigment concentration (PWC) is generally preferably 18.0% or less. If the upper limit is exceeded, the coating film appearance may be reduced. More preferably, the content is 0.01 to 15.0%, and particularly preferably 0.01 to 13.0%.
  • the water-based colored paint can contain other curing agents as long as the curing of the present invention is not inhibited.
  • the other curing agent those commonly used in paints can be used in combination other than the above-mentioned hydrophobic melamine rosin water dispersion. Examples thereof include block isocyanate, epoxy compound, aziridine compound, carpositimide compound, oxazoline compound, metal ion, and hydrophilic melamine resin.
  • Various performances and cost points of the obtained coating film Amino resin and cocoon or block isocyanate resin are generally used.
  • the block isocyanate is obtained by adding a blocking agent having active hydrogen to a polyisocyanate such as trimethylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate. And those that can be dissociated by heating to generate isocyanate groups.
  • a blocking agent having active hydrogen such as trimethylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate.
  • the content thereof is preferably 10 to: LOO parts by mass with respect to 100 parts by mass of the resin solid content in the water-based colored paint. Outside the above range, curability may be insufficient.
  • the water-based colored paint may contain other film-forming resin if necessary.
  • Other coating film-forming resins are not particularly limited, and other coatings such as acrylic resins, polyester resins, alkyd resins, epoxy resins, urethane resins other than the above-mentioned acrylic resins are used. Film-forming rosin can be used.
  • the above-mentioned other film-forming resin may have a number average molecular weight of 3,000 to 50,000, preferably 6,000 to 30,000. If it is less than 3000, workability and curability are sufficient. On the other hand, if it exceeds 50000, the non-volatile content at the time of painting will be too low and the workability may be reduced.
  • the above other upper film-forming resin has an acid value of 10 to: LOOmgKOHZg, more preferably 20 to 80 mgKOHZ g
  • the water resistance of the coating film is lowered and the lower limit is lowered. If it rotates, the water dispersibility of coconut oil may be reduced.
  • the upper limit of 20 to 180, more preferably 30 to 160 is exceeded, the water resistance of the coating film decreases, and when the lower limit is exceeded, the curability of the coating film may decrease. .
  • the blend ratio of the acrylic resin emulsion in the water-based colored paint and the other film-forming resin is 5 to 95 mass% of acrylic resin emulsion based on the total solid content of the resin. %, preferably 10 to 85 wt%, more preferably 20 to 70 wt%, other film-forming ⁇ is 95-5 wt 0/0, preferably from 90 to 15 weight 0/0, further good It is preferably 80-30% by mass. If the ratio of acrylic resin emulsion is less than 5% by mass, the workability is lowered, and if it is more than 95% by mass, the film forming property may be deteriorated.
  • water-soluble acrylic resin As the other film-forming resin, it is preferable to use water-soluble acrylic resin from the viewpoint of compatibility with the acrylic resin emulsion at the time of baking the coating film.
  • the water-soluble acrylic resin can be obtained by carrying out solution polymerization with the above-mentioned carboxylic acid group-containing unsaturated monomer as an essential component and other a, ⁇ -ethylenically unsaturated monomers.
  • When used as a water-based paint composition it contains 65% by mass or more of (meth) acrylic acid ester having 1 or 2 carbon atoms in the ester part, which is used to obtain the water-soluble acrylic resin. It is preferable from the viewpoint of the appearance of the coating film that can be obtained.
  • the water-soluble acrylic resin is usually a basic compound such as monomethylamine, dimethylamine, trimethylamine, triethylamine, diisopropylamine, monoethanolamine, diethanolamine and dimethylethanolamine. Neutralizing with an organic amine such as min and dissolving it in water This neutralization may be performed on the water-soluble acrylic resin itself or at the time of production of the water-based colored paint.
  • the water-based colored paint may contain a polyether polyol.
  • the coating film performance can be further improved.
  • the polyether polyol has at least one primary hydroxyl group in one molecule. It is preferable to use one having a number average molecular weight of 300 to 3000, a hydroxyl value of 30 to 700, and a water tolerance of 2.0 or more. If the above conditions are not satisfied, the water resistance may not be lowered or the target appearance may not be improved.
  • Such a polyether polyol is a compound obtained by adding an alkylene oxide such as ethylene oxide or propylene oxide to an active hydrogen-containing compound such as a polyhydric alcohol, polyhydric phenol, or polyhydric carboxylic acid.
  • an active hydrogen-containing compound such as a polyhydric alcohol, polyhydric phenol, or polyhydric carboxylic acid.
  • the polyether polyol is more preferably 3 to 30% by mass, preferably 1 to 40% by mass in the solid content of the coating resin.
  • viscosity control agents can be added to the above-mentioned water-based colored paint in order to prevent familiarity with the top coat and to ensure coating workability.
  • viscosity control agent those generally showing thixotropy can be used.
  • crosslinked or non-crosslinked succinic particles fatty acid amide swelling dispersions, amide fatty acids, long-chain polyaminoamide phosphates, etc.
  • Polyamide-based materials polyethylene-based materials such as colloidal swelling dispersion of acid-polyethylene, organic acid smectite clay, organic bentonite-based materials such as montmorillonite, inorganic pigments such as aluminum silicate and barium sulfate A flat pigment that develops viscosity depending on the shape of
  • the above-mentioned water-based colored paint is blended with additives usually added to the paint, for example, a surface conditioner, a thickener, an antioxidant, an ultraviolet ray inhibitor, an antifoaming agent and the like. Also good. These compounding amounts are within the range known to those skilled in the art.
  • the method for producing the above-mentioned water-based colored paint is not particularly limited, including those described later, and is well known to those skilled in the art such as kneading and dispersing a compound such as a pigment using a kneader or a roll. The method can be used.
  • the water-based colored paint can be suitably used as a water-based base paint for automobiles. Therefore, it can be applied to a method for forming a multilayer coating film applied to automobile bodies, parts and the like.
  • Examples of the method for forming the multilayer coating film include those described above for the object to be coated.
  • a process of forming a base paint film by applying a water-based colored paint (I) a process of forming a clear paint film by applying a clear paint on the base paint film without curing the base paint film (i),
  • the step (III) of simultaneously heating the base coating film and the clear one coating film can be cited.
  • the above-mentioned multi-layer coating film forming method can be used for various substrates such as metal moldings, plastic moldings, foams, etc. It is preferable to apply to paintable metal molded products.
  • Examples of the metal molded product include, for example, plates, molded products of iron, copper, aluminum, tin, zinc, and the like and alloys containing these metals, and specifically, passenger cars, trucks, motorcycles. And car bodies and parts such as buses. These metals are preferably pre-treated with phosphate, chromate, etc.
  • An electrodeposition coating film may be formed on the metal molded article subjected to the chemical conversion treatment.
  • a cation type and a charon type can be used. From the viewpoint of anticorrosion, a cation type electrodeposition paint composition is preferred.
  • plastic molded products examples include polypropylene resin, polycarbonate resin, urethane resin, polyester resin, polystyrene resin, ABS resin, vinyl chloride resin, polyamide resin, etc. Specific examples include automobile parts such as a boiler, a bumper, a mirror cover, a grill, and a door knob. Furthermore, these plastic molded products are preferably those washed with steam or neutral detergent with trichloroethane. Further, primer coating for enabling electrostatic coating may be applied.
  • an intermediate coating film may be formed on the object to be coated.
  • An intermediate coating is used to form the intermediate coating.
  • This intermediate coating contains a film-forming resin, a curing agent, various organic and inorganic coloring components, extender pigments, and the like.
  • the film-forming resin and curing agent are not particularly limited, and specific examples include the film-forming resin and curing agent mentioned in the previous water-based coloring paint. It is used. From the viewpoint of performance and cost of the resulting intermediate coating film, acryl resin and Z or polyester resin are combined with amino resin and Z or isocyanate. Used together.
  • Examples of the coloring component contained in the intermediate coating composition include those described in the previous aqueous coloring coating composition.
  • flat pigments such as aluminum powder and my power flour may be added.
  • additives that are usually added to the paint such as surface conditioners, antioxidants, antifoaming agents, etc., may be blended in the intermediate coating.
  • the film thickness of the coating film at the time of coating with the water-based colored paint is preferably a force that varies depending on the desired use. If the dry film thickness is less than 10 m, the substrate cannot be concealed, resulting in film breakage. If the film thickness exceeds 30 m, the sharpness may be reduced, or defects such as unevenness or sagging may occur during painting. May occur. In order to obtain a multilayer coating film having a good appearance, it is preferable to heat the obtained base coating film at 40 to 100 ° C. for 2 to 10 minutes before applying the clear paint.
  • the method for forming a multi-layer coating film comprises the steps of: applying the clear coating material on the base coating film obtained by applying the water-based colored coating material (water-based base coating material) without heat curing; It forms a coating film.
  • the clear one coating film smoothes and protects irregularities, flickering, and the like caused by the base coating film, and further gives an aesthetic appearance.
  • the clear one paint is not particularly limited, and a clear one paint containing a film-forming resin and a curing agent can be used. Furthermore, it is possible to include a coloring component as long as it does not hinder the design of the base.
  • Examples of the form of the clear paint include a solvent type, an aqueous type and a powder type.
  • Preferred examples of the solvent-type clear one paint include transparency or acid etching resistance.
  • a combination of an acrylic resin and Z or polyester resin and an amino resin and Z or isocyanate, or a carboxylic acid or an epoxy resin having an epoxy curing system and Z or polyester resin, etc. be able to.
  • the film-forming resin contained in the solvent-type clear paint is neutralized with a base to make it water-based.
  • the thing containing fat can be mentioned.
  • This neutralization can be carried out by adding tertiary amines such as dimethylethanolamine and triethylamine before or after polymerization.
  • thermosetting powder coating is preferred because a coating film having good physical properties can be obtained.
  • thermosetting powder coatings include epoxy-based, acrylic-based, and polyester-based powder clear paints. Particularly, acrylic-based powder clear paints with good weather resistance are particularly preferred. I like it.
  • a viscosity control agent is added to the clear one paint in order to ensure coating workability.
  • the viscosity control agent those generally showing thixotropy can be used.
  • a known force can be used.
  • it can contain a curing catalyst, a surface conditioner and the like.
  • the clear paint used in the above-mentioned multilayer coating film forming method is 20-50 seconds in Ford Cup No. 4 at 20 ° C from the viewpoint of the effect on the environment due to the content of the organic solvent. It is preferably a solvent-type clear one paint, a water-based clear one paint, or a powder-type clear one paint having a clear one paint solid content of 50% by mass or more when diluted to have a viscosity.
  • Specific examples of the method of applying the above clear paint to the base coating film include a micro-microbell and a coating method using a rotary atomizing electrostatic coating machine called a microbell. .
  • the dry film thickness of the clear coating film formed by applying the clear paint is generally 10 to 80 / ⁇ ⁇ force S, and more preferably 20 to 60 m. When the dry film thickness is less than 10 m, it is not possible to conceal the underlying unevenness, and when it exceeds 80 m, there is a risk of problems such as scratches or sagging during painting.
  • the clear coating film thus formed forms a cured coating film by simultaneously heating together with the previously formed base coating film.
  • the heat curing temperature is preferably set to 80 to 180 ° C, more preferably 120 to 160 ° C, from the viewpoint of curability and physical properties of the resulting multilayer coating film. .
  • the heat curing time can be arbitrarily set according to the above temperature. It is appropriate that the heat curing temperature is 120 ° C to 160 ° C and the time is 10 to 30 minutes.
  • the method for forming a multilayer coating film also comprises forming the intermediate coating film on the object to be coated to form an intermediate coating film, and then heating and curing the intermediate coating film (aqueous base coating). (Paint) can be applied to form a base coating, and then the above clear coating can be applied to form a clear coating, and these can be cured by heating. .
  • aqueous base coating aqueous base coating
  • the film thickness of the multilayer coating film thus obtained is generally 30 to 300 m, preferably 50 to 250 ⁇ m.
  • the film thickness is less than 30 ⁇ m, the strength of the film itself decreases, and when it exceeds 300 m, film physical properties such as a cooling cycle may decrease.
  • the multilayer coating film thus obtained is also one aspect of the present invention.
  • a coated product having a multilayer coating film obtained by the above-described multilayer coating film forming method has a multilayer coating film having extremely high glitter and color development, recoat adhesion, chipping resistance, and water resistance adhesion on the surface thereof. It is what you have.
  • the water-based colored paint of the present invention was obtained by mixing and heating a film-forming resin containing a specific acrylic resin emulsion, a specific acrylic resin and a hydrophobic melamine resin with a specific composition.
  • Hydrophobic melamine resin having a particle size of 20 to 140 nm obtained by water-dispersing the heated product and a pigment containing a curing agent and a pigment. It is possible to obtain a film.
  • the hydrophobic melamine rosin water dispersion has a specific particle size obtained by a specific production method, it has excellent storage stability, and as an optional curing agent. It can be used suitably.
  • a water-based colored paint containing the hydrophobic melamine rosin water dispersion as a curing agent is used, a coating film having excellent adhesion and surface smoothness is obtained. Can do.
  • the water-based colored paint can be suitably used as a water-based base paint.
  • the water-based colored paint of the present invention has the above-described configuration, a coating film having excellent color developability can be obtained.
  • a coating film having excellent recoat adhesion, chipping property, water-resistant adhesion property, and coloring property can be obtained.
  • this reaction vessel was charged with 23.54 parts of ethyl acrylate, 1.86 parts of 2-hydroxyethyl methacrylate, 4.60 parts of methacrylic acid, 0.2 part of Aqualon HS-10 and 10 parts of ion-exchanged water.
  • 8-ethylenically unsaturated monomer mixture (monomer mixture (b)) and 0.06 parts ammonium persulfate and 10 parts ion-exchange water initiator solution Add dropwise in parallel at 80 ° C for 0.5 hours. After completion of dripping, ripened at the same temperature for 2 hours o
  • this reaction vessel is composed of 25.3 parts of butyl methacrylate, 2.4 parts of 2-hydroxyethyl methacrylate, 2.3 parts of methacrylic acid, 1 part of Aqualon HS-10, and 24.7 parts of ion-exchanged water.
  • the solution was added dropwise in parallel at 80 ° C for 0.5 hours. After completion of the dropwise addition, aging was performed at the same temperature for 2 hours.
  • this reaction vessel also has 19.85 parts of butyl methacrylate, 2.48 parts of 2-hydroxyethyl acrylate, 7.67 parts of methacrylic acid, 1 part of Aqualon HS-10 and 14.7 parts of ion-exchanged water.
  • the second stage ⁇ , j8-ethylenically unsaturated monomer mixture (monomer mixture (f)) and an initiator solution consisting of 0.08 parts ammonium persulfate and 7.4 parts ion-exchanged water The solution was added dropwise in parallel at 80 ° C for 0.5 hours. After completion of the dropwise addition, ripening was carried out at the same temperature for 2 hours.
  • Emulsion resin E m-c with non-volatile content 30%, solid content acid value 50mgKOHZg, hydroxyl value 40 is obtained.
  • this reaction vessel was charged with 18.08 parts butyl methacrylate, 10.54 parts 2-hydroxyethyl acrylate, 1.38 parts methacrylic acid, 0.1 part Aqualon HS-10 and 24.7 parts ion-exchanged water.
  • Second stage ⁇ j8-ethylenically unsaturated monomer mixture (monomer mixture) Compound (h)), 0.08 parts of ammonium persulfate and 7.4 parts of a strong initiator solution were added dropwise in parallel at 80 ° C. for 0.5 hours. After completion of the dropwise addition, aging was performed at the same temperature for 2 hours.
  • reaction vessel 28.31 parts of butyl methacrylate, 0.31 part of 2-hydroxyethyl acrylate, 1.38 parts of methacrylic acid, 0.1 part of Aqualon HS-10 and 24.7 parts of ion-exchanged water.
  • Second stage ⁇ j8-ethylenically unsaturated monomer mixture (monomer mixture (j)), ammonium persulfate 0.08 parts and ion-exchanged water 7.4 parts initiator solution Were dripped in parallel at 80 ° C. over 0.5 hours. After completion of the dropwise addition, ripening was carried out at the same temperature for 2 hours.
  • the mixture was adjusted to pH 6.5 with 2.14 parts of ion exchange water and 0.224 part of dimethylaminoethanol, and an average particle size of 80 ⁇ m, Non-volatile content 30%, solid content acid value 9mgKOHZg, hydroxyl value 5 emulsion resin
  • the pH was adjusted to 6.5 with the addition of 2.14 parts of ion-exchanged water and 0.332 parts of dimethylaminoethanol, and an average particle size of 80 ⁇ m, non-volatile content 30%, solid content acid value 30mgKOHZg, hydroxyl value 40 emulsion resin E m- g.
  • Emulsion resin Em-i having a non-volatile content of 30%, a solid content acid value of 10 mgKOHZg, and a hydroxyl value of 35 was protected.
  • the first stage ⁇ —ethylenically unsaturated monomer mixture (monomer mixture (r)) and Ammonia persulfate (0.21 parts) and ion-exchanged water (8.60 parts) of the initiator solution were dropped into the reaction vessel in parallel over 2 hours. After completion of the dropping, aging was performed at the same temperature for 1 hour.
  • emulsion resin Em-j having an average particle size of 80 ⁇ m, non-volatile content of 30%, solid content acid value of 10mgKOHZg, and hydroxyl value of 35. 7
  • Table 1 Average particle diameter, acid value (AV), hydroxyl value (OHV), acid value of shell part, synthesis method (2) stage emulsion polymerization or single-stage emulsion polymerization), collectively shows shell amount in the acrylic ⁇ emulsion (mass 0/0).
  • MFDG methyl propylene diglycol, manufactured by Nippon Emulsifier Co., Ltd.
  • MFDG methyl propylene diglycol, manufactured by Nippon Emulsifier Co., Ltd.
  • acrylic acid 32.48 parts of 2-hydroxyethyl methacrylate, 47.75 parts of butyl acrylate, MSD-100-methylstyrene dimer, manufactured by Mitsui Chemicals, Inc.
  • an initiator solution consisting of 0.5 parts of Caester O and 5 parts of MFDG was added dropwise over 0.5 hours. After completion of the dropwise addition, aging was performed at the same temperature for 1 hour.
  • Table 2 summarizes the particle sizes of the melamine greaves water dispersions obtained in the above production examples.
  • an initiator solution of 5.0 parts dipropylene glycol methyl ether and 0.3 parts t-butylperoxy-2-ethylhexanoate was added dropwise to the reaction vessel over 0.5 hours. After completion of the dropping, aging was performed at the same temperature for 2 hours.
  • the obtained acrylic resin solution had a non-volatile content of 30.0%, a solid content acid value of 40 mg KOHZg, and a hydroxyl value of 50.
  • EFKA4550 F-Power, on-type pigment dispersant, trade name.
  • Aqueous base paints b to; j were obtained in the same manner as in Example 1 except that the types of the acrylic resin emulsion and the melamine resin aqueous dispersion were changed as shown in Table 4.
  • Aqueous base paint 1 was obtained in the same manner as Paint Comparative Example 1 except that Em-b was used instead of the acrylic resin emulsion Em-a of Paint Comparative Example 1.
  • a water-based base paint n was obtained in the same manner as in Paint Comparative Example 3 except that Em-b was used in place of the acrylic resin emulsion Em-a in Paint Comparative Example 3.
  • the aqueous base paints a to q obtained in Examples and Comparative Examples were each applied to a steel plate with a doctor blade 20 mil and baked at 140 ° C. for 30 minutes to form a coating film.
  • the color developability (white blur feeling, bluish feeling) of the obtained coating film was visually evaluated according to the following criteria. The results are shown in Table 4.
  • A 0 to 50% or less.
  • ⁇ Over 50% and 100% or less.
  • Baking and drying were performed for 30 minutes, and a coating test plate of 2 coats and 1 beta (2C1B) was prepared as a coating method, and left for 30 minutes in a desiccator.
  • the cured coatings with base paint and clear paint were painted so that the dry film thicknesses were 15 m and 40 ⁇ m, respectively.
  • the coating test plate obtained by forming the multilayer coating film was evaluated for chipping resistance as follows. Using a grave mouth tester (manufactured by Suga Test Instruments Co., Ltd.), 100 g of No. 7 crushed stone was impinged on the coating film at an angle of 30 ° with an air pressure of 3. OkgfZcm 2 from a distance of 35 cm. After washing and drying, a peel test was performed using an industrial gum tape manufactured by Chiban Co., Ltd., and then the degree of peeling of the coating film was visually observed and evaluated.
  • the coating test plate obtained by forming the multilayer coating film is immersed in 40 ° C warm water for 10 days, and after 1 hour of washing, the water resistance of the test plate is evaluated and the initial recoat adhesion (NSR property) is evaluated.
  • the method was evaluated by the method described in 2).
  • the water-based base paints obtained in the examples were able to obtain a coating film having excellent color developability. Moreover, in the formation of the multilayer coating film using the aqueous base paint obtained in the examples, a multilayer coating film excellent in initial recoat adhesion, chipping resistance, and water adhesion resistance could be obtained. On the other hand, the comparative example of the paint was unsatisfactory to satisfy all these requirements.
  • ⁇ -ethylenically unsaturated monomer mixture (monomer mixture (a)): 23.1 parts acrylic acid, 32.48 parts 2-hydroxyethyl methacrylate, 39.4 parts butyl acrylate, MS D— 100-methylstyrene dimer (Mitsui Chemicals Co., Ltd.) Except that 5 parts were used, in the same manner as in Production Example 11, non-volatile content 60%, solid content acid value 180 mgKOHZg, hydroxyl value 140, number average molecular weight (Mn) Acrylic rosin Ac2 of 3000 was obtained.
  • Table 5 shows the acrylic grease 8 obtained in the above production example. -& Oihi 7 ⁇ 2 ⁇ 8. The acid value (eight), hydroxyl value (OHV), and number average molecular weight (Mn) of 6 are shown together.
  • Production Example 22 Akles 3 ⁇ 4
  • a saturated monomer mixture (monomer mixture (c)) and 0.21 part of ammonium persulfate and an initiator solution of 8.6 parts of ion-exchanged water were added dropwise to the reaction vessel in parallel over 2 hours. After completion of the dropwise addition, aging was performed at the same temperature for 1 hour.
  • reaction vessel was charged with a second stage ⁇ , j8-ethylenically unsaturated monomer mixture consisting of 23.54 parts of ethyl acrylate, 1.86 parts of 2-hydroxyethyl methacrylate and 4.60 parts of methacrylic acid.
  • (Monomer mixture (d)) and 0.08 parts ammonium persulfate and 7.4 parts initiator solution with ion exchange water were added dropwise in parallel at 80 ° C. for 0.5 hours. After completion of the dropwise addition, aging was performed at the same temperature for 2 hours.
  • hydrophobic melamine rosin water dispersions MFD-b, MFD-a, and MFD-c produced in Production Examples 13, 12, and 14 were referred to as Examples 1, 2, and 3, respectively.
  • Each hydrophobic melamine rosin aqueous dispersion was allowed to stand at 40 ° C. for 1 month, and changes in the dispersion were visually evaluated.
  • Each hydrophobic melamine rosin aqueous dispersion was applied to a steel plate with a doctor blade 20 mil. Adhesion was evaluated by the following method after drying at 140 ° C for 30 minutes.
  • Example 1 MFD-b Ac-a U20SB 9.6 1 5/85 80 ° C 4h 40 ° C 80nm 0 ⁇ ⁇
  • Example 2 MFD-a Ac-a U20SB 9.6 1 5/85 80 ° C 2h 40 ° C 1 20nm ⁇ 0 ⁇
  • Example 3 MFD-c Ac-a U20SB 9.6 30/70 80 ° C 4h 40 ° C 50nm ⁇ ⁇ ⁇ Implementation
  • Example 4 MFD-1 ⁇ Ac2 U20SB 9.6 1 5/85 80.
  • Comparative Example MFD-8 A-1 U28-70W 9.8 60/40 70 ° C 4h 40 ° C 1 80nm 0 o Comparative Example 8 MFD-9 A-1 U28-70W 9.8 40/60 70 ° C 4h 40. C 230nm ⁇ ⁇
  • Aqueous base paints ⁇ to ⁇ and G were obtained in the same manner as in Example 11 except that the types of the acrylic resin emulsion and the melamine resin aqueous dispersion were changed as shown in Table 7.
  • the aqueous base paints A to G obtained in the paint examples and the comparative examples were each applied to a steel plate with a doctor blade 20 mil and baked at 140 ° C. for 30 minutes to form a coating film.
  • the color developability (white blur feeling, bluish feeling) of the obtained coating film was evaluated by the same method as described above.
  • initial recoat adhesion, chipping resistance, and water adhesion were evaluated by the same methods as described above. The results are shown in Table 7.
  • the water-based colored paint of the present invention can be suitably used as a water-based base paint in automobile painting.

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  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

L'invention concerne un procédé de production de dispersion de résine de mélamine hydrophobe aqueuse à excellente capacité de stockage et pouvant donner un film de revêtement à excellent pouvoir adhésif et excellente texture de surface lisse. On décrit aussi un matériau de revêtement en couleur à base d'eau capable de donner un film de revêtement à excellentes propriétés de coloration, d'adhésion de deuxième revêtement, de résistance à l'écaillage et d'adhésion humide. Ledit matériau comprend une résine filmogène, un durcisseur et un pigment. La résine comprend une émulsion de résine acrylique produite par polymérisation d'émulsion, à valeur acide de 1-30 mg-KOH/g et valeur hydroxy de 10-150, et le durcisseur comprend une dispersion aqueuse de résine de mélamine hydrophobe dont les particules ont un diamètre de 20-140 nm.
PCT/JP2005/021056 2004-11-16 2005-11-16 Materiau de revetement en couleur a base d'eau, dispersion aqueuse de resine de melamine hydrophobe et procede de production correspondant, composition de revetement a base d'eau, et procede de formation de film multicouche WO2006054611A1 (fr)

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JP2006545104A JP5048337B2 (ja) 2004-11-16 2005-11-16 水性着色塗料、疎水性メラミン樹脂水分散体及びその製造方法、水性塗料組成物、並びに、複層塗膜形成方法

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WO2007013558A1 (fr) * 2005-07-27 2007-02-01 Nippon Paint Co., Ltd. Composition de revêtement métallique à base d'eau et procédé de formation d'un film de revêtement multicouche
JP2009530453A (ja) * 2006-03-17 2009-08-27 サイテク サーフェィス スペシャルティーズ オーストリア ゲーエムベーハー 光沢の改善されたコーティング用の水性バインダ
EP2336254A1 (fr) * 2009-12-18 2011-06-22 Basf Se Dispersions de polymères
US8492472B2 (en) 2009-12-18 2013-07-23 Basf Se Polymer dispersions for corrosion control
JP2013224387A (ja) * 2012-04-23 2013-10-31 Mitsubishi Rayon Co Ltd 重合体の分散液および製造方法
JP2018135439A (ja) * 2017-02-21 2018-08-30 日本ペイント・オートモーティブコーティングス株式会社 水性塗料組成物および複層塗膜
CN109777227A (zh) * 2019-01-25 2019-05-21 广东嘉盛环保高新材料股份有限公司 一种车辆用水性色漆及其制备方法
CN112724760A (zh) * 2020-12-29 2021-04-30 富思特新材料科技发展股份有限公司 一种耐沾污涂料及其制备方法和应用

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WO2007013558A1 (fr) * 2005-07-27 2007-02-01 Nippon Paint Co., Ltd. Composition de revêtement métallique à base d'eau et procédé de formation d'un film de revêtement multicouche
JP2009530453A (ja) * 2006-03-17 2009-08-27 サイテク サーフェィス スペシャルティーズ オーストリア ゲーエムベーハー 光沢の改善されたコーティング用の水性バインダ
US8519043B2 (en) 2009-12-18 2013-08-27 Basf Se Polymer dispersions
RU2555027C2 (ru) * 2009-12-18 2015-07-10 Басф Се Полимерные дисперсии
WO2011073341A3 (fr) * 2009-12-18 2011-10-20 Basf Se Dispersions de polymères
CN102666752A (zh) * 2009-12-18 2012-09-12 巴斯夫欧洲公司 含聚合物分散体的单组分/双组分涂料物质以及其制备方法和其用于防腐中的用途
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US8492472B2 (en) 2009-12-18 2013-07-23 Basf Se Polymer dispersions for corrosion control
EP2336254A1 (fr) * 2009-12-18 2011-06-22 Basf Se Dispersions de polymères
WO2011080067A3 (fr) * 2009-12-18 2011-09-15 Basf Se Dispersions polymériques pour la protection contre la corrosion
CN102666751B (zh) * 2009-12-18 2014-12-24 巴斯夫欧洲公司 聚合物分散体
JP2013224387A (ja) * 2012-04-23 2013-10-31 Mitsubishi Rayon Co Ltd 重合体の分散液および製造方法
JP2018135439A (ja) * 2017-02-21 2018-08-30 日本ペイント・オートモーティブコーティングス株式会社 水性塗料組成物および複層塗膜
JP2022075758A (ja) * 2017-02-21 2022-05-18 日本ペイント・オートモーティブコーティングス株式会社 水性塗料組成物および複層塗膜
JP7090399B2 (ja) 2017-02-21 2022-06-24 日本ペイント・オートモーティブコーティングス株式会社 水性塗料組成物および複層塗膜
US11518890B2 (en) 2017-02-21 2022-12-06 Nippon Paint Automotive Coatings Co., Ltd. Water-based coating composition, and multi-layer coating film
JP7360490B2 (ja) 2017-02-21 2023-10-12 日本ペイント・オートモーティブコーティングス株式会社 水性塗料組成物および複層塗膜
CN109777227A (zh) * 2019-01-25 2019-05-21 广东嘉盛环保高新材料股份有限公司 一种车辆用水性色漆及其制备方法
CN112724760A (zh) * 2020-12-29 2021-04-30 富思特新材料科技发展股份有限公司 一种耐沾污涂料及其制备方法和应用

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