CN103649247A - Multicomponent water-based colored base-coat paint composition - Google Patents

Multicomponent water-based colored base-coat paint composition Download PDF

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Publication number
CN103649247A
CN103649247A CN201280031818.9A CN201280031818A CN103649247A CN 103649247 A CN103649247 A CN 103649247A CN 201280031818 A CN201280031818 A CN 201280031818A CN 103649247 A CN103649247 A CN 103649247A
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China
Prior art keywords
composition
water
viscous regulator
methyl
resin
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CN201280031818.9A
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Inventor
柳口刚男
西泽安明
藤田裕介
平野昌典
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Kansai Paint Co Ltd
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Kansai Paint Co Ltd
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Publication of CN103649247A publication Critical patent/CN103649247A/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • 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
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4202—Two or more polyesters of different physical or chemical nature
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters
    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Dispersion Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Paints Or Removers (AREA)

Abstract

A multicomponent water-based colored base-coat paint composition containing a water-diluted resin component (A), a pigment (B), a poly(meth)acrylate-based viscosity modifier (C), and water. Said water-diluted resin component (A) comprises a combination of the following: a base component (I) containing a water-diluted urethane resin; and a viscosity-modifier component (II) containing a poly(meth)acrylate-based viscosity modifier and a water-diluted acrylic resin. This makes it possible to provide a multicomponent water-based colored base-coat paint composition that yields a colored base coat that exhibits excellent coating properties and a stable finished appearance and is extremely drip-resistant.

Description

The water-based pigmented basecoat coating composition of multicomponent system
Technical field
The present invention relates to the water-based pigmented basecoat coating composition of multicomponent system.
Background technology
In recent years, in the fields such as automobile or car repair application, the market of water-based pigmented basecoat coating is expansion energetically.
Known, in the application of water-based pigmented basecoat coating, finished appearance is easily subject to the impact of temperature or the humidity of painting environment, particularly the in the situation that of containing metal pigment, the degree, flickering, particle sense etc. of speckle of filming have a great difference along with painting environment, be difficult to obtain the application of stable finished appearance.
In patent documentation 1, record a kind of water-based paint compositions, it is by the bottom coating composition that contains resin, pigment, tackifier and water and contain water and the thinner of tackifier forms, even metallic paint, formed finished appearance of filming etc. are also fine, are subject to the impact of painting environment little.
In patent documentation 2, record a kind of water-based paint compositions, it is by the special effect pigments composition that contains water reducible resin and contain inorganic laminated silicate, water-dilutable urethane resin and water but containing the composition of pigment, do not form, it has suitable rheological, good to the resistivity of coating flowing hanging.
In patent documentation 3, record a kind of water-borne coatings, the part of its part by the water-based special-effect that contains special effect pigments, water reducible binder, organic solvent, water and lacquer additive and the tackiness agent that contains water-dilutable polyurethane binder, water, organic solvent and oil paint additive forms, and can reach high efficiency production and storage.
Like this, by multicomponent system, form water-based pigmented basecoat coating and use a class not only containing water but also containing tackifier or the composition of the water reducible binder such as urethane is known technology for adjusting the thinner of dope viscosity.
On the other hand, a kind of water-based paint compositions that contains water dispersible acrylate copolymer (A), waterborne polyurethane resin (B) and negatively charged ion core shell resin dispersion (C) is disclosed in patent documentation 4, and recorded adopt that said composition can form that hidden power is high, tack, water tolerance and good the filming of sharpening.
But, in car repair application, when the body of a motor car completing being carried out to Repair Coatings in order to make the old coating film of Repair Coatings position and body of a motor car there is equal finished appearance, can not at high temperature be dried, in order to avoid the parts such as equipment of interior of body are affected.In addition, with industrial paint line also require painting environment stably the situation in span of control compare, between each Repair Coatings scene, there is very big-difference, therefore it is very difficult, designing a kind of water-based pigmented basecoat coating that can give finished appearance that meets whole Repair Coatings scene.
From above-mentioned viewpoint, consider, in order to reduce the solids component of the water-based pigmented basecoat coating using in application, be divided into 4～5 left and right and carry out application, in every 1 application, by with air blast (with air gun etc. to painting face blowing compressed air gently) by dried coating film, with the sagging that improves the viscosity of filming and suppress to film, by the same coating of application repeatedly of filming to this, formation pigmented basecoat is filmed, this is practical situation, therefore, in order to improve operating efficiency, require to shorten or omit the operation of blowing.
But, if use the composition of recording in patent documentation 1～4, the operation of not blowing but carry out continuously application, adopt the wet coating that repeats that wet method is carried out same coating of cover, formedly film or sagging occurs, or generation speckle, can not form uniformly and film, will film be impregnated into water in after, tend to expand, can not get satisfied film performance.
Prior art document
Patent documentation
Patent documentation 1: JP 2006-70095 communique
Patent documentation 2: JP 2001-316612 communique
Patent documentation 3: Unexamined Patent 6-340830 communique
Patent documentation 4: JP 2010-037516 communique
Summary of the invention
Invent problem to be solved
The object of the invention is to, the water-based pigmented basecoat coating composition of a class multicomponent system is provided, this coating composition can form a kind of resistance to flow pigmented basecoat very good and that have stable finished appearance and a good Physical properties of coating film and film.
For solving the means of problem
The inventor etc. have carried out meticulous research to above-mentioned problem, found that, by water-based pigmented basecoat coating composition being divided into the host composition (I) that contains water-dilutable urethane resin, pigment and poly-(methyl) acrylic acid series viscous regulator and containing water-dilutable acrylic resin and the viscous regulator composition (II) of poly-(methyl) acrylic acid series viscous regulator, resistance to flow in the time of can increasing substantially application, and can obtain stable finished appearance and film performance, thereby complete the present invention.
Therefore, the invention provides following technical scheme.
1, the water-based pigmented basecoat coating composition of multicomponent system, it is combined by host composition (I) and viscous regulator composition (II),
Host composition (I) contains water reducible resin composition (A), pigment (B), poly-(methyl) acrylic acid series viscous regulator (C) and water, and water reducible resin composition (A) contains by water-dilutable urethane resins more than solid component meter 30 quality % the part as this composition in composition (A) solids component; The amount of the effective constituent of poly-(methyl) acrylic acid series viscous regulator (C) is with respect to the solids component of water reducible resin composition (A) in the scope in 0.01～5.0 quality %;
Viscous regulator composition (II) contains water reducible resin composition (D), poly-(methyl) acrylic acid series viscous regulator (E) and water, and water reducible resin composition (D) contains by water-dilutable acrylic resins (d1) more than solid component meter 50 quality % the part as this composition in (D) composition solids component.
2, the water-based pigmented basecoat coating composition of the system of the multicomponent described in technical scheme 1, wherein, water reducible resin composition (A) in host composition (I), except water-dilutable urethane resin, also contains water-soluble acrylic resin and acrylic resin emulsion.
3, the water-based pigmented basecoat coating composition of the system of the multicomponent described in technical scheme 1 or 2, wherein, the mass ratio of host composition (I) and viscous regulator composition (II), take that they add up to 100 mass parts as benchmark, in the scope of composition (I) in 40～95 mass parts, in the scope of composition (II) in 5～60 mass parts.
4, the water-based pigmented basecoat coating composition of the system of the multicomponent described in wantonly 1 of technical scheme 1～3, wherein, the multicomponent system that it forms for also combine viscous regulator composition (III) except host composition (I) and viscous regulator composition (II), it is viscous regulator (F) and water that this viscous regulator composition (III) contains inorganic.
5, the water-based pigmented basecoat coating composition of the system of the multicomponent described in technical scheme 4, wherein, viscous regulator composition (III) also contains water reducible resin composition (G).
6, the water-based pigmented basecoat coating composition of the system of the multicomponent described in technical scheme 5, wherein, the water reducible resin composition (G) in viscous regulator composition (III) contains water-dilutable urethane resin as a part for this composition.
7, the water-based pigmented basecoat coating composition of the system of the multicomponent described in wantonly 1 of technical scheme 4～6, wherein, viscous regulator composition (III) also contains pigment.
8, the water-based pigmented basecoat coating composition of the system of the multicomponent described in wantonly 1 of technical scheme 4～7, wherein, the mass ratio of host composition (I), viscous regulator composition (II) and viscous regulator composition (III), take that they add up to 100 mass parts as benchmark, in the scope of composition (I) in 30～80 mass parts, in the scope of composition (II) in 1～40 mass parts, in the scope of composition (III) in 0.5～50 mass parts.
The effect of invention
Water-based pigmented basecoat coating composition of the present invention is by the host composition (I) that contains water-dilutable urethane resin and pigment and contains water-dilutable acrylic resin and the viscous regulator composition (II) of poly-(methyl) acrylic acid series viscous regulator formation, the Combination of the two is good, the water-based pigmented basecoat coating composition being formed by their hybrid modulation, can form also good filming of the very good and finished appearance of resistance to flow.In addition, about the water-based pigmented basecoat coating composition of invention described in technical scheme 4, the Combination of each composition is also good, can form all good filming of the good and resistance to flow of painting operation, finished appearance.
In addition, this water-based pigmented basecoat coating composition is because its resistance to flow is very good, therefore, even in the situation that shorten or cut down the air blowing operation between each application and repeat to be continuously coated with same coating composition, when application, filming not can sagging, and there is hardly speckle etc., and can form good finished appearance, can cut down time and energy required when forming undercoat and filming.
Embodiment
Water-based pigmented basecoat coating composition of the present invention is combined by host composition (I) and viscous regulator composition (II).
< < host composition (I) > >
Host composition (I) in the present invention is characterised in that, it contains water reducible resin composition (A), pigment (B), poly-(methyl) acrylic acid series viscous regulator (C) and water, water reducible resin composition (A) contains by water-dilutable urethane resins more than solid component meter 30 quality % the part as this composition in composition (A) solids component, and the amount of the effective constituent of poly-(methyl) acrylic acid series viscous regulator (C) is with respect to the solids component of water reducible resin composition (A) in the scope in 0.01～5.0 quality %.
Be explained, in this specification sheets, solids component refers to nonvolatile component, refers to from sample except anhydrating, the residue after the volatile component such as organic solvent, can calculate by the quality of sample is multiplied by solid component concentration.Solid component concentration can be by approximately 3 grams, sample is measured divided by the quality before dry 105 ℃ of residual quality of dry 3 hours, and, sometimes also with percentage, recently represent.
Residue after the thinners such as in addition, effective constituent refers to from sample except anhydrating, organic solvent.
< water reducible resin composition (A) >
As water reducible resin composition (A), so long as resinous principle that can dilute with water is just not particularly limited, can use known material, method for making etc. in the past, can milli unrestrictedly use the resin of water-soluble, emulsion-type or colloid decentralized.As resin kind, such as the modified resin etc. that can enumerate acrylic resin, urethane resin, vibrin, Synolac, silicone resin, celluosic resin, these resins, they can use separately, also can use by multiple combination.
In the present invention, the water reducible resin composition (A) containing in host composition (I) is characterised in that, in this composition (A) solids component, contain by more than solid component meter 30 quality %, preferably more than 40 quality %, more preferably water-dilutable urethane resin more than 45 quality %.
If the content of water-dilutable urethane resin is lower than 30 quality %, tack, water tolerance that the undercoat being formed by water-based pigmented basecoat coating composition of the present invention is filmed become not so good, and the opacifying power that undercoat is filmed also has the tendency of reduction, be therefore undesirable.
As this water-dilutable urethane resin, can unrestrictedly use resin well known in the art by milli, for example, can be by making the polyurethane prepolymer being formed by polymeric polyisocyanate, polyvalent alcohol and the diol reaction that contains carboxyl disperse to obtain in water.
As polymeric polyisocyanate, can enumerate the aliphatic diisocyanate compounds such as hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, dimer acid diisocyanate, lysinediisocyanate, the biuret type affixture of these diisocyanate cpds, isocyanurate ring affixture, isophorone diisocyanate, 4,4-methylene-bis (cyclohexyl isocyanate), methylcyclohexane-2,4-(or-2,6-) vulcabond, 1,3-(or Isosorbide-5-Nitrae-) two (isocyanide acyl methyl) hexanaphthene, Isosorbide-5-Nitrae-cyclohexyl diisocyanate, 1,3-pentamethylene vulcabond, 1, the alicyclic diisocyanate compounds such as 2-cyclohexyl diisocyanate, the biuret type affixture of these vulcabond, isocyanurate ring affixture, Xylene Diisocyanate, m xylene diisocyanate, tetramethylxylene diisocyanate, tolylene diisocyanate, 4, 4-diphenylmethanediisocyanate, 1, 5-naphthalene diisocyanate, 1, 4-naphthalene diisocyanate, 4, 4-Tolylamine vulcabond, 4, 4-diphenyl ether isocyanic ester, (m-or p-) phenylene vulcabond, 4, 4-biphenylene vulcabond, 3, 3-dimethyl-4, 4-biphenylene vulcabond, two (4-isocyanide acyl phenyl) sulfone, the aromatic diisocyanate compounds such as isopropylidene two (4-phenyl isocyanate), the biuret type affixture of these diisocyanate cpds, isocyanurate ring affixture, triphenyl methane-4,4,4-triisocyanate, 1,3,5-tri-isocyanide acyl benzene, 2,4,6-tri-isocyanide acyl toluene, 4,4-dimethyl diphenylmethane-2,2,5,5-tetraisocyanate etc. have the polyisocyanate compounds of more than 3 isocyanate group in 1 molecule, the biuret type affixture of these polyisocyanate compounds, isocyanurate ring affixture, by the polyvalent alcohols such as ethylene glycol, propylene glycol, BDO, dimethylol propionic acid, polyalkylene glycol, TriMethylolPropane(TMP), hexanetriol and polyisocyanate compounds, according to isocyanate group, with respect to the hydroxyl of above-mentioned polyvalent alcohol, be that excessive ratio is reacted the polyurethane-reinforcement affixture forming, the biuret type affixture of these polyurethane-reinforcement affixtures, isocyanurate ring affixture etc.
As above-mentioned polyvalent alcohol, the for example polyvalent alcohol of number-average molecular weight in 200～10000 scopes can be used, the polyether glycols such as polyoxyethylene glycol, polypropylene glycol, polyethylene-propylene (block or random) glycol, polytetramethylene ether diol, polyhexamethylene ether glycol, poly-eight methylene ether glycol can be enumerated, by di-carboxylic acid (hexanodioic acid, succsinic acid, sebacic acid, pentanedioic acid, toxilic acid, fumaric acid, phthalic acid etc.) with glycol (ethylene glycol, propylene glycol, 1, 4-butyleneglycol, 1, 6-hexylene glycol, 3-methyl isophthalic acid, 5-pentanediol, dimethyltrimethylene glycol, two methylol hexanaphthenes etc.) polyvalent alcohol that polycondensation forms, polyethylene glycol adipate for example, poly adipate succinic acid ester, poly-hexanodioic acid hexylene glycol ester, poly-neo-pentyl adipic acid ester, poly--3-methyl amyl adipic acid ester, poly-adipate glycol/butanediol ester, the polyester polyols such as poly-neo-pentyl/hexyl adipic acid ester, ester polyol in polycaprolactone polyol, poly--3-methylpent, polycarbonate polyol, ethylene glycol, glycol ether, triglycol, 1,2-propylene glycol, 1, the low molecular weight diols classes such as 4-butyleneglycol, tetramethylene glycol, hexamethylene glycol, decamethylene glycol, ethohexadiol, tristane two methylols, Hydrogenated Bisphenol A, cyclohexanedimethanol, 1,6 hexylene glycol, Deng, they can use separately or two or more merges use.
As above-mentioned carboxylic dibasic alcohol, for example can enumerate dihydroxymethyl acetic acid, dimethylol propionic acid, dimethylolpropionic acid etc.
In the manufacture of above-mentioned polyurethane prepolymer, the condition of the equivalence ratio that the mixing ratio of mentioned component preferably makes isocyanate group/hydroxyl in 1.1～1.9 scope coordinates.The building-up reactions of prepolymer can be carried out based on known method in the past.
Above-mentioned water-dilutable urethane resin can neutralize with neutralizing agent.As this neutralizing agent, so long as carboxyl can be neutralized, be just not particularly limited, for example can enumerate sodium hydroxide, potassium hydroxide, Trimethylamine 99, dimethylaminoethanol, 2-methyl 2-amino-1-propyl alcohol, triethylamine, ammonia etc.
Above-mentioned water-dilutable urethane resin can be the state being scattered in water, as its median size, and can be in 0.01～1 μ m, particularly preferably in the scope in 0.05～0.5 μ m.In this specification sheets, first median size refers to dilutes sample with deionized water, then uses submicron particle size measure of spread device " COULTER N4 type " (Beckman Coulter company system) at the numerical value of 20 ℃ of mensuration.
In the present invention, about above-mentioned water-dilutable urethane resin, from the storage stability viewpoint of host composition (I), consider, be preferably solids component acid number and be 5～100mgKOH/g, the preferred resin within the scope of 10～70mgKOH/g.
In addition, the water reducible resin composition (A) in host composition (I), except above-mentioned water-dilutable urethane resin, preferably also contains water-dilutable acrylic resin, for example, and water-soluble acrylic resin and acrylic resin emulsion.
As water-soluble acrylic resin, for example can enumerate, utilize polymerization starter to make to contain polymerizability unsaturated monomer, the polymerizability unsaturated monomer of hydroxyl and the polymerizability unsaturated monomer composition of other polymerizability unsaturated monomer containing acidic group polymerization and the resin that obtains under the existence of hydrophilic organic solvent.
As the above-mentioned polymerizability unsaturated monomer containing acidic group, for example can enumerate the carboxylic polymerizability unsaturated monomers such as vinylformic acid, methacrylic acid, β-crotonic acid, toxilic acid, methylene-succinic acid, β-propyloic acrylic ester; 2-acrylamide-2-methyl propane sulfonic, allyl sulphonic acid, styrene sulfonic acid sodium salt, methacrylic acid sulfo group ethyl ester and sodium salt and ammonium salt etc. are containing sulfonic polymerizability unsaturated monomer; The polymerizability unsaturated monomers of the phosphorous acidic groups such as 2-acryloxy ethyl acid phosphoric acid ester, 2-methacryloxyethyl acid phosphoric acid ester, 2-acryloxy propyl group acid phosphoric acid ester, 2-methacryloxypropyl acid phosphoric acid ester etc., they can use separately separately or two or more is merged and is used.
As the polymerizability unsaturated monomer of above-mentioned hydroxyl, can enumerate (methyl) acrylic acid hydroxy alkyl ester of 2～8 of the carbon numbers such as (methyl) HEA, (methyl) vinylformic acid 2-hydroxypropyl ester, (methyl) vinylformic acid 3-hydroxypropyl ester, (methyl) hydroxybutyl acrylate; N hydroxymethyl acrylamide; Allyl alcohol; The 6-caprolactone modified acrylic acid monomer of (methyl) acrylic acid hydroxy alkyl ester that carbon number is 2～8; Polyalkylene glycol (methyl) acrylate such as glycol ether (methyl) acrylate, triglycol (methyl) acrylate, polyoxyethylene glycol (methyl) acrylate, dipropylene glycol (methyl) acrylate, tripropylene glycol (methyl) acrylate, polypropylene glycol (methyl) acrylate, polyoxyethylene glycol polypropylene glycol (methyl) acrylate etc., they can use separately separately or two or more is merged and is used.
As above-mentioned other polymerizability unsaturated monomer, can enumerate (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) vinylformic acid pentyl ester, (methyl) Ethyl acrylate, (methyl) Octyl acrylate, (methyl) 2-EHA, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) dodecylacrylate ((methyl) vinylformic acid Lauryl Ester), (methyl) tridecyl acrylate, (methyl) stearyl acrylate base ester, (methyl) vinylformic acid iso stearyl ester, (methyl) cyclohexyl acrylate, (methyl) acrylic methyl cyclohexyl, (methyl) vinylformic acid tertiary butyl cyclohexyl, (methyl) vinylformic acid cyclo-dodecyl ester, (methyl) isobornyl acrylate, (methyl) vinylformic acid adamantane esters, (methyl) acrylic acid alkyl or the cycloalkyl esters such as (methyl) vinylformic acid three ring decyl ester, (methyl) benzyl acrylate, vinylbenzene, alpha-methyl styrene, Vinyl toluene etc. are containing the polymerizability unsaturated monomer of aromatic ring, vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxy ethoxy) silane, γ-(methyl) acryloxy propyl trimethoxy silicane, γ-(methyl) acryloxy propyl-triethoxysilicane etc. have the polymerizability unsaturated monomer of alkoxysilyl, (methyl) perfluoroalkyl acrylate such as (methyl) vinylformic acid perfluoro butyl ethyl ester, (methyl) vinylformic acid perfluoro capryl ethyl ester, fluoroolefins etc. have the polymerizability unsaturated monomer of fluoro-alkyl, dimaleoyl iminos etc. have the polymerizability unsaturated monomer of optical polymerism functional group, the vinyl compounds such as NVP, ethene, divinyl, chloroprene, vinyl propionate base ester, vinyl-acetic ester, (methyl) vinylformic acid allyl ester, two (methyl) vinylformic acid glycol ester, two (methyl) vinylformic acid triethyleneglycol ester, two (methyl) vinylformic acid Tetraglycol 99 ester, two (methyl) vinylformic acid 1, 3-butanediol ester, trimethylolpropane tris (methyl) acrylate, two (methyl) vinylformic acid 1, 4-butanediol ester, two (methyl) vinylformic acid dimethyltrimethylene glycol ester, two (methyl) vinylformic acid 1, 6-hexylene glycol ester, two (methyl) vinylformic acid pentaerythritol ester, four (methyl) vinylformic acid pentaerythritol ester, two (methyl) vinylformic acid glyceryl ester, 1, 1, 1-trimethylolethane two (methyl) acrylate, 1, 1, 1-trimethylolethane trimethacrylate (methyl) acrylate, 1, 1, 1-trimethylolpropane tris (methyl) acrylate, isocyanuric acid triallyl ester, diallyl terephthalate, Vinylstyrenes etc. at least have the polymerizability unsaturated monomer of 2 polymerizability unsaturated groups in 1 molecule, (methyl) vinyl cyanide, (methyl) acrylamide, N, N-dimethylaminoethyl (methyl) acrylate, N, N-diethyl aminoethyl (methyl) acrylate, N, the nitrogenous polymerizability unsaturated monomers such as affixture of N-dimethyl aminopropyl (methyl) acrylamide, (methyl) vinylformic acid glycidyl esters and amine, (methyl) vinylformic acid glycidyl esters, (methyl) vinylformic acid Beta-methyl glycidyl esters, (methyl) vinylformic acid 3,4-epoxy group(ing) cyclohexyl methyl ester, (methyl) vinylformic acid 3,4-epoxy group(ing) cyclohexyl ethyl ester, (methyl) vinylformic acid 3, the polymerizability unsaturated monomer that 4-epoxy group(ing) cyclohexyl propyl diester, allyl glycidyl ether etc. contain epoxy group(ing), (methyl) vinylformic acid 2-isocyanide acyl ethyl ester, m-pseudoallyl-alpha, alpha-dimethylbenzyl isocyanic ester etc. are containing the polymerizability unsaturated monomer of isocyanide acyl group, molecular end is (methyl) acrylate with polyoxyethylene ethylidene chain of alkoxyl group, polymerizability unsaturated monomer that propenal, diacetone-acryloamide(DAA), diacetone Methacrylamide, methacrylic acid acetoacetoxy groups ethyl ester, formyl radical vinylbenzene, the vinyl alkyl ketone (for example, ethenyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone) etc. with 4～7 carbon atoms contain carbonyl etc.These polymerizability unsaturated monomers can be used separately separately or two or more is used in combination.
In addition, in order to improve the water-soluble of this resin and in order to improve the finished appearance of water-based pigmented basecoat coating composition of the present invention, above-mentioned water-soluble acrylic resin preferably neutralizes acidic group with neutralizing agent.As this neutralizing agent, as long as being just not particularly limited of acidic group can being neutralized for example can be enumerated sodium hydroxide, potassium hydroxide; The amine compound such as Trimethylamine 99, dimethylaminoethanol, 2-methyl-2-amino-1-propyl alcohol, triethylamine; Ammoniacal liquor etc.
As above-mentioned water-soluble acrylic resin, in general, its solids component acid number is 5～100mgKOH/g, is preferably the scope of 10～70mgKOH/g; Solids component hydroxyl value is 10～150mgKOH/g, is preferably the scope of 20～100mgKOH/g; Weight-average molecular weight is 5000～10,0000, is preferably in 8,000～70,000 scope.
In this specification sheets, weight-average molecular weight is for by with gel permeation chromatography (Tosoh(strain) company's system, " HLC8120GPC ") weight-average molecular weight of mensuration is according to take the value that the weight-average molecular weight of polystyrene is basis conversion.As chromatographic column, use " TSKgel G-4000H * L ", " TSKgel G-3000H * L ", " TSKgel G-2500H * L ", " TSKgel G-2000H * L " (being Tosoh(strain) company's system, trade(brand)name) 4, according to moving phase: tetrahydrofuran (THF); Measure temperature: 40 ℃; Flow velocity: 1ml/ divides; The condition of detector: RI is carried out.
In addition, number-average molecular weight is for by gel permeation chromatography (Tosoh(strain) company's system, " HLC8120GPC ") number-average molecular weight measured is according to take the value that the number-average molecular weight of polystyrene is basis conversion.As chromatographic column, use " TSKgel G-4000H * L ", " TSKgelG-3000H * L ", " TSKgel G-2500H * L ", " TSKgel G-2000H * L " (being Tosoh(strain) company's system, trade(brand)name) 4, according to moving phase: tetrahydrofuran (THF); Measure temperature: 40 ℃; Flow velocity: 1ml/ divides, the condition of detector: RI is carried out.
As the hydrophilic organic solvent for polymerization, there is no strict difference, for example can enumerate, at 20 ℃ of organic solvents that at least dissolve 20g in 100g water, specifically can enumerate the alcohol organic solvent such as methyl alcohol, ethanol, Virahol, propyl carbinol, isopropylcarbinol; Two
Figure BDA0000447731050000111
the ether organic solvent such as alkane, tetrahydrofuran (THF); The gylcol ether organic solvents such as ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol list n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol list n-butyl ether, ethylene glycol list isobutyl ether, ethylene glycol list tertbutyl ether; The glycol ether ethers organic solvents such as diglycol monotertiary methyl ether, carbiphene, diglycol monotertiary n-propyl ether, diglycol monotertiary isopropyl ether, diglycol monotertiary n-butyl ether, diglycol monotertiary isobutyl ether, diglycol monotertiary butyl ether; The propylene glycol ethers organic solvents such as propylene glycol monomethyl ether, propylene glycol list ethyl ether, propylene glycol list n-propyl ether, propylene glycol monoisopropyl ether; The dipropylene glycol ethers organic solvents such as DPGME, dihydroxypropane single-ethyl ether, dipropylene glycol list n-propyl ether, dipropylene glycol monoisopropyl ether; The ester class organic solvents such as ethyl acetate, butylacetate, isobutyl acetate, 3-methoxyl group butylacetic acid ester etc., they can use separately or two or more is used in combination.
As polymerization starter, can use without restriction known initiator in the past, for example can enumerate Cyclohexanone peroxides, 3,3,5-trimethyl hexanone peroxide, methyl cyclohexanone peroxide, two (tert-butyl hydroperoxide)-3,3 of 1,1-, 5-trimethyl-cyclohexane, two (tert-butyl hydroperoxide) hexanaphthenes of 1,1-, normal-butyl-4, two (tert-butyl hydroperoxide) valerates of 4-, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydro-peroxidase, two (a tert-butyl hydroperoxide-sec.-propyl) benzene of 1,3-, 2,5-dimethyl-2,5-bis-(tert-butyl hydroperoxide) hexane, diisopropyl benzene superoxide, tertiary butyl cumyl peroxide, decanoyl superoxide, lauroyl peroxide, benzoyl peroxide, 2,4-dichlorobenzoperoxide, two t-amyl peroxy things, two (tert-butylcyclohexyl) peroxy dicarbonate, tert butyl peroxy benzoate, 2,5-dimethyl-2,5-bis-(benzoyl peroxidation) hexane, the peroxide polymerization starters such as tert-butyl hydroperoxide-2-ethylhexanoate, 2, 2-azo two (isopropyl cyanide), 2, 2-azo is two-2-methylbutyronitrile, 1, 1-azo two (hexanaphthene-1-nitrile), azocumene, 2, 2-azo two (2-methylbutyronitrile), 2, 2-azo two-2, 4-methyl pentane nitrile, 4, 4-azo two (4-cyanopentanoic acid), 2-(tertiary butyl azo)-2-dicyanopropane, 2, 2-azo two (2, 4, 4-trimethylpentane), 2, 2-azo two (2-methylpropane), 2, two (2-methyl-N-(2-hydroxyethyl)-propionic acid amides of 2-azo), dimethyl 2, 2-azo two (2 Methylpropionic acid ester), 1, 1-azo two (1-hexanaphthene-1-nitrile), 2, two (2-(2-tetrahydroglyoxaline-2-yl) propane of 2-azo), dimethyl-2, the azo polymerization starters such as 2-azo-bis-isobutyrate.
As aforesaid propylene acid resin emulsion, can be the acrylic resin emulsion beyond above-mentioned water-soluble acrylic resin, can use aptly for example by adopting 1 step or multi-step to make polymerizability unsaturated monomer composition carry out the resin emulsion that letex polymerization obtains under the existence at water and dispersion stabilizer.
As polymerizability unsaturated monomer composition, can enumerate with explanation at above-mentioned water-soluble acrylic resin in the same monomer component of the monomer of example, when adopting multi-step to carry out letex polymerization, can suitable adjustment monomer composition and the ratio of the total usage quantity of the polymerizable monomer that uses in this step.
In addition, as for making acrylic resin emulsion carry out the dispersion stabilizer of letex polymerization, be not particularly limited, for example can enumerate, nonionic emulsifier such as anionic emulsifier, the senior alcohol ether of polyoxyethylene and polyoxyethylene alkyl phenyl ether such as dialkyl sodium sulfosuccinate, Sodium dodecylbenzene sulfonate, Sodium Lauryl Sulphate BP/USP, polyoxyethylene alkyl phenyl ether sodium sulfate and alkyl diphenyl base ether sodium disulfonate and have the anionic of free-radical polymerised pair of key or cationic reactive emulsifier, they also can merge use.
Reactive emulsifier refers in molecule, jointly to have wantonly more than a kind group and the emulsifying agent of polymerizability unsaturated group in non-ionic type group, anionic group and cationic group; as polymerizability unsaturated group; specifically can enumerate (methyl) allyl group, (methyl) acryl, propenyl, butenyl etc.As commercially available product, can enumerate " LATEMUL " (trade(brand)name, flower king (strain) system), " ELEMINOL " (trade(brand)name, Sanyo change into (strain) system), " Aqualon " (trade(brand)name, first industrial pharmacy (strain) system), " Adelcuria soap " (trade(brand)name, rising sun electrification (strain) system), " ANTOX " (trade(brand)name, Japanese emulsifying agent (strain) system) etc.
In the present invention, as contained acrylic resin emulsion in host composition (I), the viewpoint of making the tack film and water retting of filming from undercoat is considered, preferably under the existence of water and emulsifying agent, preferred reactive emulsifying agent, with 1 step, make polymerizability unsaturated monomer composition carry out letex polymerization and the acrylic resin emulsion of the single-layer type that obtains.
As this polymerizability unsaturated monomer that is aggregated into single-layer type acrylic resin emulsion, suitablely comprise containing the polymerizability unsaturated monomer of acidic group, the polymerizability unsaturated monomer of hydroxyl, carbon number are more than 6 straight chain shape or the polymerizability unsaturated monomer containing alkyl of a chain and other polymerizability unsaturated monomers.
As containing the polymerizability unsaturated monomer of acidic group and the polymerizability unsaturated monomer of hydroxyl, can enumerate and above-mentioned same compound.
In addition, the polymerizability unsaturated monomer containing alkyl as carbon number at more than 6 straight chain shapes or a chain, can enumerate the just own ester of (methyl) vinylformic acid, (methyl) Octyl acrylate, (methyl) 2-EHA, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) tridecyl acrylate, (methyl) vinylformic acid Lauryl Ester, (methyl) stearyl acrylate base ester, " vinylformic acid iso stearyl ester " (Osaka organic chemistry society system) etc., they can use separately separately or two or more is used in combination.
As the water-soluble acrylic resin in above-mentioned water reducible resin composition (A) and the usage ratio of acrylic resin emulsion, the finished appearance of filming from the storage stability of host composition (I), the undercoat that adopts continuous finishing to obtain and the viewpoint of water tolerance are considered, water-soluble acrylic resin/acrylic resin emulsion is by solids component mass ratio, be suitably 10/90～80/20, be preferably 25/75～60/40 scope.
< pigment (B) >
In the present invention, the pigment (B) as contained in above-mentioned host composition (I), can be used known pigment in the past without restriction.As its concrete example, can enumerate combined oxidation metallic pigment, carbon black, azo pigment, quinoline Azone class pigment, diketopyrrolo-pyrrole class pigment, perylene class pigment, pyrene ketone pigment, benzoglyoxaline ketone pigment, isoindoline class pigment, isoindoline ketone pigment, metallo-chelate azo pigment, phthalocyanine pigment, the indanthrone class pigment, two such as the metal oxide pigments such as titanium oxide, ferric oxide, titan yellow
Figure BDA0000447731050000141
the tinting pigments such as alkanes pigment, indigo class pigment; Aluminium (comprising AM aluminum metallization), copper, zinc, brass, nickel, aluminum oxide, mica, with titanium oxide or the coated aluminum oxide of ferric oxide, with photoluminescent pigment such as titanium oxide or the coated mica of ferric oxide, glass fragment, holography (Holograno) pigment; The pigment extenders such as clay, kaolin, barium sulfate, barium carbonate, calcium carbonate, talcum, silicon-dioxide, white lake (alumina white); Deng, according to the color or the film performance that become target, they can use separately separately or two or more is used in combination.
In addition, in the situation that making with light Hui pigment, its shape is not particularly limited, and preference is as flakey, and considers from suppressing to produce the viewpoint of hydrogen, preferably with containing phosphate or sulfonic treatment agent, carries out dispersion treatment and is coated.Contain in phosphate or sulfonic treatment agent, can not be subject to particular restriction and use known low molecular compound or multipolymer in the past.
Use level as pigment (B), according to target, tint and the pigment that uses and different, in general, from the viewpoint of paint stability, suitable is, solids component with respect to resin contained in host composition (I) adds up to 100 mass parts, is preferably in the scope of 0.1～300 mass parts, more preferably in the scope of 0.5～200 mass parts.The method that this pigment (B) is coupled in host composition (I) is not particularly limited, but in the situation that host composition (I) contains water-soluble acrylic resin, should in advance pigment (B) be mixed with this resin and water, conditioned pigment dispersion, and then this pigment dispersion is mixed with other compositions, be coupled in host composition (I).
< gathers (methyl) acrylic acid series viscous regulator (C) >
In the present invention, host composition (I) contains poly-(methyl) acrylic acid series viscous regulator (C) as viscous regulator, to host composition (I) can stably be preserved, and can form and can not produce filming of speckle or sagging etc., good finished appearance by the water-based pigmented basecoat coating composition being obtained by mixing with viscous regulator composition (II).As this poly-(methyl) acrylic acid series viscous regulator (C), can use without restriction known viscous regulator in poly-(methyl) sodium acrylate, polyacrylic acid-paint field such as (methyl) acrylate copolymer.
Commercially available product as this poly-(methyl) acrylic acid series viscous regulator, for example can enumerate " SN Thickener613 ", " the SN Thickener618 " of " Primal ASE60 ", " the Primal TT615 " of Rohm and Haas company system, " Primal RM5 " (being trade(brand)name above), Sannopco society system, " SN Thickener630 ", " SN Thickener634 ", " SN Thickener636 " (being trade(brand)name above) etc.
As the effective constituent acid number of this poly-(methyl) acrylic acid series viscous regulator, be 30～300mg/KOH, be preferably in the scope of 80～280mg/KOH.
In the present invention, the amount of the effective constituent of contained poly-(methyl) acrylic acid series viscous regulator (C) in host composition (I), solids component with respect to water reducible resin composition (A), suitable is in the scope of 0.01～5.0 quality %, preferably in the scope of 1.0～4.5 quality %.Poly-(methyl) acrylic acid series viscous regulator (C) if the amount of effective constituent lower than 0.01 quality %, the storage stability of host composition (I) is good not, or in order to shorten or to cut down air blowing operation between each application and continuously during application water-based pigmented basecoat coating composition, its resistance to flow is good not, if the amount of the effective constituent of poly-(methyl) acrylic acid series viscous regulator (C) surpasses 5.0 quality %, host composition (I) is insufficient with the Combination of viscous regulator composition described later (II), and the finished appearance of filming obtaining is undesirable, particularly in the situation that using metal coating composition, can produce speckle etc., therefore be undesirable.
Above-mentioned host composition (I) also can contain known viscous regulator in addition of pigment dispersing agent, UV light absorber, photostabilizer, polymer particles, dispersing auxiliary, sanitas, silane coupling agent, defoamer, curing catalysts, wetting agent, poly-(methyl) acrylic acid series viscous regulator (C), organic solvent, neutralizing agent etc. and other the composition such as normally used additive for coatings when modulation water-borne coatings.
The solid component concentration of above-mentioned host composition (I) is different with the difference of tinting, in general, from the viewpoint of painting operation and covering property and finished appearance, consider, suitable is at 15～50 quality %, preferably in the scope of 20～40 quality %, adjust.
In addition, viscosity as above-mentioned host composition (I), be not particularly limited, from storage stability with the blended viewpoint of viscous regulator composition described later (II) etc., consider, be 100～2000mPasec, preferably 600～2000mPasec, more preferably in the scope of 800～1600mPasec.In this specification sheets, so-called viscosity, refer to by sample after 25 ℃ of modulation at 10 minutes with the interior value that digital VismetronVDA type viscometer (sesame pumping system Co., Ltd. system) is measured under speed of rotation 60rpm condition with viscometer.
< < viscous regulator composition (II) > >
In the present invention, viscous regulator composition (II) contains water reducible resin composition (D), poly-(methyl) acrylic acid series viscous regulator (E) and water.
In the present invention, by viscous regulator composition (II) being mixed in above-mentioned host (I) before facing application, can control according to painting environment the rheological properties of water-based pigmented basecoat coating composition, by formation water-based pigmented basecoat coating composition like this, even if can form storage stability that a class can keep each composition, while, the in the situation that of application continuously, also sagging, speckle etc. can not occur, and the good undercoat of finished appearance is filmed.
< water reducible resin composition (D) >
As the water reducible resin composition (D) that allows to contain in viscous regulator composition (II), in the compound of the illustrated example of water reducible resin composition (A) that can be contained from above-mentioned host composition (I), suitable selection is used.By making viscous regulator composition (II) contain water reducible resin composition (D), can make the Combination of itself and host composition (I) good, and the undercoat being formed by the water-based pigmented basecoat coating composition phenomenons such as producing speckle of filming reduces, and make it have good finished appearance.
Feature of the present invention is, water reducible resin composition (A) contained in host composition (I) contains by water-dilutable urethane resins more than solid component meter 30 quality % the part as this composition in its composition (A) solids component, and in viscous regulator composition (II), contained water reducible resin composition (D) contains by more than solid component meter 50 quality %, more preferably water-dilutable acrylic resins (d1) more than 60 quality % is as a part for this composition in its composition (D) solids component.
If water-dilutable acrylic resin (d1) content, lower than 50 quality %, often produces speckle etc. on undercoat is filmed, this is undesirable.
In addition, in viscous regulator composition (II), when water reducible resin composition (D) contains water-dilutable urethane resin, its content is preferably pressed solid component meter lower than 30 quality % in this composition (D) solids component, particularly preferably lower than 20 quality %, further preferably lower than 1%.
As above-mentioned water-dilutable acrylic resin (d1), preferably contain the water-soluble acrylic resin as this composition part.By containing water-soluble acrylic resin, appropriateness can become so that the viscosity of the viscous regulator composition (II) that contains poly-(methyl) acrylic acid series viscous regulator can excessively not rise, good with the Combination of host composition (I), there is hardly sagging etc. in the water-based pigmented basecoat coating composition obtaining, can form the undercoat that finished appearance is good and film.
As this water-soluble acrylic resin, can use without restriction known resin in the past, can from the explanation of above-mentioned host composition (I), in the water-soluble acrylic resin of example, select to use aptly, and, host composition (I) can with contained water-soluble acrylic resin-phase in viscous regulator composition (II) with.
As the content of water-soluble acrylic resin contained in above-mentioned water-dilutable acrylic resin (d1), in this (d1) solids component, by solid component meter, can be more than 40 quality %, preferably in the scope of 45～95 quality %.
In addition, in viscous regulator composition (II), contained water-dilutable acrylic resin (d1) preferably contains acrylic resin emulsion as a part for this composition.
As this acrylic resin emulsion, can use without restriction known resin emulsion in the past, can from the explanation of above-mentioned host composition (I), in the acrylic resin emulsion of example, select to use aptly, and host composition (I) can be identical with acrylic resin emulsion contained in viscous regulator composition (II).
In the present invention, as contained acrylic resin emulsion in viscous regulator composition (II), preferably its solids component hydroxyl value be 40mgKOH/g following, be particularly preferably 20mgKOH/g following, more preferably below 5mgKOH/g, its solids component acid number is 1～50mgKOH/g, be preferably the core-shell-type acrylic resin emulsion in the scope of 5～30mgKOH/g.
By making viscous regulator composition (II) and poly-(methyl) acrylic acid series viscous regulator (E) described later all contain aforesaid propylene acid resin emulsion, can make the Combination of itself and host (I) become good, and can make resistance to flow or the finished appearance of water-based pigmented basecoat coating composition when continuous application become good, in addition, also there is the effect that improves the water tolerance that pigmented basecoat films.
The polymerizability unsaturated monomer using during as manufacture aforesaid propylene acid resin emulsion, can enumerate above-mentioned monomer, as preferred monomer, can enumerate the polymerizability unsaturated monomer containing aromatic ring.
As the above-mentioned polymerizability unsaturated monomer containing aromatic ring, can enumerate vinylbenzene, alpha-methyl styrene, Vinyl toluene etc.
In above-mentioned core-shell-type acrylic resin emulsion, as the monomer component that forms core, preferably contain 15～80 quality % containing the polymerizability unsaturated monomer of aromatic ring, and the content of the contained polymerizability unsaturated monomer containing aromatic ring of core is preferably more than the content of the contained polymerizability unsaturated monomer containing aromatic ring of shell portion.
In addition, as core and the contained total amount containing the polymerizability unsaturated monomer of aromatic ring of the both sides of shell portion, be preferably the scope of 15～80 quality %.
In addition, the mixing ratio of core and shell portion, by core/shell portion mass ratio, is suitably 5/95～95/5, preferably in 10/90～90/10 scope.
In addition, as the dispersion stabilizer using when the above-mentioned core-shell-type acrylic resin emulsion polymerization, can enumerate above-mentioned dispersion stabilizer, and consider from the viewpoint of undercoat water-resistance property of coating, preferably use reactive emulsifier.
As the content of acrylic resin emulsion contained in above-mentioned water-dilutable acrylic resin (d1), more than preferably its quality is counted 50 quality % in this (d1) solids component by solids component, preferably in the scope more than 60 quality %.
< gathers (methyl) acrylic acid series viscous regulator (E) >
In the present invention, viscous regulator composition (II) contains poly-(methyl) acrylic acid series viscous regulator (E).By making viscous regulator composition (II) contain poly-(methyl) acrylic acid series viscous regulator, can obtain the effect of the resistance to flow that improves water-based pigmented basecoat coating composition of the present invention.
As poly-(methyl) acrylic acid series viscous regulator (E), can use with host composition (I) in the same material of contained poly-(methyl) acrylic acid series viscous regulator (C).
Active constituent content as poly-(methyl) acrylic acid series viscous regulator (E) in viscous regulator composition (II), the quality of viscous regulator composition (II) of take is benchmark, from undercoat, film continuous application time the viewpoint of resistance to flow, finished appearance consider, should be 0.01～5%, preferably in 0.05～3% scope.
Above-mentioned viscous regulator composition (II) also can contain known viscous regulator in addition of pigment, pigment dispersing agent, UV light absorber, photostabilizer, polymer particles, dispersing auxiliary, sanitas, silane coupling agent, defoamer, curing catalysts, wetting agent, poly-(methyl) acrylic acid series viscous regulator (E), organic solvent, neutralizing agent etc. and other the composition such as the additive for coatings that conventionally uses when modulation water-borne coatings.
In addition, from the viewpoint of painting operation, covering property and finished appearance, consider, the solid component concentration of viscous regulator composition (II) is generally in 0.5～30 quality %, preferably in the scope in 1～15 quality %.
Viscosity as above-mentioned viscous regulator composition (II), be not particularly limited, from the storage stability of viscous regulator composition (II) and with the blended viewpoint of host composition (I), consider, should be 100～2500mPasec, be preferably 300～2300mPasec, more preferably in the scope of 400～2100mPasec.
< < viscous regulator composition (III) > >
Water-based pigmented basecoat coating composition of the present invention, except above-mentioned host composition (I) and viscous regulator composition (II), can also further be combined to form multicomponent system with viscous regulator composition (III), i.e. 3 composition systems.
By further combining with viscous regulator composition (III), can improve resistance to flow and the finished appearance of water-based pigmented basecoat coating composition, and, also can appropriateness adjust the viscosity of water-based pigmented basecoat coating composition, make application become easier.
As this viscous regulator composition (III), be the composition of the composition different from above-mentioned host composition (I), viscous regulator composition (II), wish that for containing inorganic be the composition of viscous regulator (F) and water.
< is inorganic is viscous regulator (F) >
As above-mentioned inorganic be viscous regulator (F), can use conditioning agent well known in the art, for example can enumerate, layer silicate mineral and silicon dioxide microparticle etc., they can be any in natural product, synthetics, processing treatment product.As concrete example, can enumerate montmorillonite, beidellite, nontronite, saponite, hectorite, humite (stevensite), mica and wilkinite etc.They also can dilute by diluent media such as organic solvent or water.
As commercially available product, can enumerate " Bentone27 ", " Bentone34 ", " Bentone38 ", " Bentone SD-1 ", " Bentone SD-2 ", " Bentone SD-3 ", " Bentone52 ", " Bentone57 " (being above Rheox company system, trade(brand)name); " Tixogel VP ", " Tixogel TE ", " Tixogel UN ", " Tixogel EZ100 ", " Tixogel MP100 ", " Tixogel MP250 " (being above Sud Chemical company system, trade(brand)name); " Claytone40 ", " Claytone34 ", " Claytone HT ", " Claytone APA ", " Claytone AF ", " Claytone HY " (being above Southern Clay Products company system, trade(brand)name); " Aerosil RX200 ", " Aerosil R812 ", " Aerosil R805 ", " Aerosil RY200 ", " Aerosil R202 " (being above Japanese Aerosil Co., Ltd. system, trade(brand)name); " Laponite RD ", " Laponite RDS " (trade(brand)name, Wilbur-Ellis society system) etc.
Resistance to flow from water-based pigmented basecoat coating composition when the continuous application, the viewpoint of finished appearance are considered, as inorganic in viscous regulator composition (III), it is the active constituent content of viscous regulator (F), when viscous regulator composition (III) does not contain water reducible resin composition described later (G), the quality of viscous regulator composition (III) of take is benchmark, should be 0.1～3.0 quality %, preferably in the scope of 0.3～2.0 quality %; And when viscous regulator composition (III) contains water reducible resin composition described later (G), as inorganic in viscous regulator composition (III), it is the active constituent content of viscous regulator (F), the solids component of water reducible resin composition (G) of take is benchmark, should be 1～25 quality %, preferably in the scope of 3～20 quality %.
< water reducible resin composition (G) >
In the present invention, from the film performances such as water tolerance and resistance to flow, particularly the viewpoint of resistance to flow during application is considered continuously, above-mentioned viscous regulator composition (III) preferably also contains water reducible resin composition (G).
Water reducible resin composition (G) as contained in viscous regulator composition (III), is not particularly limited, and can enumerate the same compound of compound of example in the explanation with above-mentioned water reducible resin composition (A).
In the present invention, the water reducible resin composition (G) in viscous regulator composition (III) preferably contains water-dilutable urethane resin as a part for this composition.
By making viscous regulator composition (III) contain water-dilutable urethane resin, can make the storage stability of viscous regulator (III) become good, and no matter contained pigment is any kind in host composition (I), tinting during water-based pigmented basecoat coating composition of continuous application wide region, all can obtain the effect that resistance to flow is stable.
As this water-dilutable urethane resin, can be from the explanation of above-mentioned host composition (I) select aptly to use in the resin of example, and contained water-dilutable urethane resin can be identical in host composition (I) and viscous regulator composition (III).
As the content of the contained water-dilutable urethane resin of water reducible resin composition (G), in this composition (G) solids component, water-dilutable urethane resin solids component is more than 40 quality %, preferably in the scope more than 50 quality %.
In addition, the effect easily expanding from improving the resistance to flow of water-based pigmented basecoat coating composition when the application continuously and finished appearance and wetted perimeter, in addition, also have the aspect considerations such as effect of the covering property of filming, viscous regulator composition (III) preferably contains pigment.
As this pigment, can use without restriction known pigment in the past, particularly, as pigment (B), can enumerate the pigment of above-mentioned example.
The color harmony orientation of especially never filming to undercoat brings disadvantageous effect and considers with the Combination of host composition (I) and viscous regulator composition (II) also good viewpoint, as this pigment, preferably uses pigment extender.
Consumption as above-mentioned pigment, the viewpoint of the resistance to flow from water-based pigmented basecoat coating composition when the continuous application, finished appearance, covering property is considered, when viscous regulator composition (III) does not contain water-dilutable resinous principle (G), viscous regulator composition (III) quality of take is benchmark, should be 0.05～10 quality %, preferably in the scope of 0.05～5 quality %; When viscous regulator composition (III) contains water reducible resin composition (G), as the pigment content in viscous regulator composition (III), the solids component quality of water reducible resin composition (G) of take is benchmark, should be 0.5～100 quality %, preferably in the scope of 0.5～50 quality %.
In addition, above-mentioned viscous regulator composition (III) can contain the polyol compound with polyalkylene skeleton.
As the polyol compound with polyalkylene skeleton, for example can enumerate, in glycol ether, triglycol, Tetraglycol 99, polyoxyethylene glycol, dipropylene glycol, polypropylene glycol, dibutylene glycol, polytetramethylene glycol, polyethylene oxide, poly-reduction propane, the block with ethylene oxide/propylene oxide or random copolymerization at least a kind of structure, polyalkylene polyvalent alcohol; By polyvalent alcohol polyvalent alcohols that form through polyalkylene modification, that contain polyalkylene skeleton such as trimethylolethane, TriMethylolPropane(TMP), poly-TriMethylolPropane(TMP), tetramethylolmethane, polypentaerythritol, Sorbitol Powder, mannitol, glycerine, Polyglycerine, polytetramethylene glycol; The polyester polyol of the condenses that the polyprotonic acids such as above-mentioned polyalkylene polyvalent alcohol and maleic anhydride, toxilic acid, fumaric acid, itaconic anhydride, methylene-succinic acid, hexanodioic acid, m-phthalic acid form; The caprolactone modification polyvalent alcohol being formed through caprolactone modification by polyether glycol; Deng.
As the above-mentioned weight-average molecular weight with the polyol compound of polyalkylene skeleton, should be 100～10000, be preferably in 400～5000 scope.
In addition, as the consumption with the polyvalent alcohol of above-mentioned polyalkylene skeleton, from using the viewpoint of the finishability of filming of bottom coating composition formation of the present invention and the storage stability of viscous regulator composition (III), consider, take in viscous regulator composition (III) contained inorganic be that the effective constituent quality of viscous regulator (F) is benchmark, should be 50～1000 quality %, preferably in the scope of 100～500 quality %.
Above-mentioned viscous regulator composition (III) also can contain UV light absorber, photostabilizer, polymer particles, dispersing auxiliary, sanitas, silane coupling agent, defoamer, curing catalysts, inorganic be viscous regulator (F) in addition known viscous regulator, organic solvent, neutralizing agent etc. and when modulation water-borne coatings other the composition such as normally used additive for coatings.
About the solid component concentration of above-mentioned viscous regulator composition (III), from the viewpoint of painting operation and covering property and finished appearance, consider, be generally adjusted to 1～30 quality %, be preferably adjusted in the scope of 5～20 quality %.
In addition, viscosity as above-mentioned viscous regulator composition (III), be not particularly limited, from the viewpoint of the storage stability of viscous regulator composition (III) and the painting operation of water-based pigmented basecoat coating composition, consider, should be 10～2000mPasec, be preferably 10～1000mPasec, more preferably in the scope of 10～600mPasec.
< < water-based pigmented basecoat coating composition > >
In the present invention, host composition (I) and viscous regulator composition (II) and the viscous regulator composition (III) using are as required taken care of respectively separately, application dealer can be uniformly mixed each composition before facing application, as required, the thinners such as water carry out viscosity adjustment, modulate thus water-based pigmented basecoat coating composition of the present invention.Be explained, in this specification sheets, the implication of facing before application do not determined entirely by application dealer or painting site, but for example can enumerate, before carrying out 3 hours of application to starting between application.
Mass ratio as the host composition (I) in above-mentioned water-based pigmented basecoat coating composition and viscous regulator composition (II), can carry out suitable adjustment according to painting environment etc., from the covering property of filming, finished appearance during continuous application and the viewpoint of resistance to flow are considered, in general, take their total 100 mass parts is benchmark, composition (I) is 40～95 mass parts, be preferably 45～90 mass parts, composition (II) is 5～60 mass parts, be preferably in the scope of 10～55 mass parts, or, as host composition (I), the mass ratio of viscous regulator composition (II) and viscous regulator composition (III), in general, take their total 100 mass parts is benchmark, composition (I) is 30～80 mass parts, be preferably 35～70 mass parts, composition (II) is 1～40 mass parts, be preferably 5～30 mass parts, composition (III) is 0.5～50 mass parts, be preferably in the scope of 5～35 mass parts.
In addition, in the present invention, can also be as required, make any in above-mentioned host composition (I), viscous regulator composition (II) and viscous regulator composition (III) contain polyisocyanate curing agent, blocked isocyanate solidifying agent, melamine solidifying agent, the solidifying agent such as azoles quinoline solidifying agent, carbodiimide solidifying agent, or use as alternative composition.
The solid component concentration of water-based pigmented basecoat coating composition of the present invention obtained above, considers from the viewpoint of painting operation and covering property and finished appearance, usually, is suitably 10～40 quality %, preferably in the scope of 15～35 quality %.
In addition, viscosity as above-mentioned water-based pigmented basecoat coating composition when the application, be not particularly limited, and then resistance to flow during from continuous application good from painting operation and the viewpoint of finished appearance are considered, be suitably 160～600mPasec, preferably in the scope of 200～500mPasec.
< < application > >
Water-based pigmented basecoat coating composition of the present invention can adopt the known application means such as spray-coating, electrostatic coating, brush application, roller coat to carry out application, from the viewpoint of the finished appearance of filming, considers, preferably carries out spray-coating.
As application number of times, can be 1 time, from having the viewpoint of finished appearance and covering property concurrently, consider, preferably by same coating repeatedly application for several times, for example, 3～6 left and right of application repeatedly.
In the present invention, the in the situation that of application repeatedly, even if omit the air blowing operation of carrying out between each application, carry out continuously application, film and also sagging can not occur, can there is good finished appearance, as required, between each application, operations such as levelling (will film after application standing at normal temperatures) also can being set, blowing or preheating.
Dry after application finishes of water-based pigmented basecoat coating composition, is not particularly limited, the in the situation that of application top layer described later varnish repeatedly, it can be undried state, but, be preferably in for example 20～100 ℃, preferably under the temperature condition of 40～100 ℃, make its dry 5～60 minutes.Thickness can be adjusted according to the state of coated surface is suitable, in general, as dry film thickness, should be 5～100 μ m, in the scope particularly preferably in 10～60 μ m.
As applicable coated surface, the coated surface that can enumerate known substrate surface in the past or arrange on this base material, as this base material, is not particularly limited, and for example can enumerate the metals such as iron, aluminium; The organic substrates such as plastics; The inanimate matter such as concrete, timber base material etc., in addition, as filming of arranging on this base material, be not particularly limited, for example can enumerate, the undercoat being formed by pigmented basecoat coating composition arranging on body of a motor car etc. is filmed and top layer varnish is coated with film formed multilayer film, the lower floor of filming at this undercoat, also can suitablely arrange bottom film, electroplate film, floating coat is filmed etc. films.
In addition, the repair paint of repairing of filming that water-based pigmented basecoat coating composition of the present invention also can be used as having formed on above-mentioned coated surface is used.In this situation, can with putty or the whole coating materials of bottom etc., to coated surface, carry out pre-treatment in advance.And, above-mentioned water-based painted in application after bottom coating composition, also can be on this be filmed application top layer varnish colour.
As described top layer varnish colour, for example, in car repair application purposes, preferably use using the acrylic resin that contains the bridging property functional groups such as hydroxyl or fluoro-resin as host, contain polymeric polyisocyanate etc. as the curable coating of solidifying agent, or preferably use and using the acrylic resin of cellulose acetate butyrate modification as the lacquer coating of principal constituent etc., in addition, also can use the coating of baking-curing types such as containing blocked isocyanate or melamine.This top layer varnish colour can further as required, contain pigment class, derivatived cellulose class, add the additive for coatings such as resin, UV light absorber, photostabilizer, surface conditioner, curing catalysts.
Embodiment
Below, with embodiment, be described more specifically the present invention.But the present invention is not limited to these embodiment.Be explained, " part " in following example and " % " represent respectively " mass parts " and " quality % ".
The manufacture > of < water-dilutable urethane resin
Production Example 1
In reaction vessel, 115.5 parts of poly adipate succinic acid esters, number-average molecular weight 2000, two ends that number-average molecular weight 2000, two ends are had to a hydroxyl have 23.2 parts of 115.5 parts of polycaprolactone glycols, the dimethylol propionic acids, 1 of hydroxyl, 120.1 parts of 6.5 parts of 4-butyleneglycols and isophorone diisocyanates join in aggregation container, under agitation, in nitrogen gas stream, at 85 ℃, reaction is carried out 7 hours, obtained the prepolymer of NCO content 4.0%.Secondly, this prepolymer is cooled to 50 ℃, add 165 parts, acetone, make after its uniform dissolution, under agitation add 15.7 parts of triethylamines, while remaining on 50 ℃, add below 600 parts of deionized waters, the water dispersion obtaining is kept 2 hours at 50 ℃, transfer reaction is stopped, then, in decompression and 70 ℃ of following distillations, remove acetone, with triethylamine and deionized water, pH value is adjusted to 8.0, obtaining solids component acid number is the ester-polyurethane resin emulsion (A-1) that 26mgKOH/g, solid component concentration are 30%.
The manufacture > of < water-soluble acrylic resin
Production Example 2
In reaction vessel, add 550 parts of propylene glycol list n-propyl ether, in nitrogen gas stream, be warming up to 115 ℃.The temperature of above-mentioned reaction vessel reaches after 115 ℃, spend 3 hours the monomer mixture that is dissolved with 10 parts of Diisopropyl azodicarboxylates in 10 parts of 350 parts of methyl methacrylates, 200 parts of n-butyl acrylates, 250 parts of 2-Ethylhexyl Methacrylates, 130 parts of vinylformic acid 4-hydroxyl butyl esters, 60 parts, vinylformic acid and " Lightester PM " (notes 1) is added in said vesse, make its slaking 2 hours.After reaction finishes, resultant is neutralized by equivalent with dimethylethanolamine, and then add 450 parts of propylene glycol list n-propyl ether, and with dimethylethanolamine, be adjusted to pH7.5, obtain yellow solution (solids component 55%) liquid, water-soluble acrylic resin (B-1).The weight-average molecular weight of water-soluble acrylic resin (B-1) is 45,000, and solids component acid number is 47mgKOH/g, and solids component hydroxyl value is 51mgKOH/g.
(note 1) " Lightester PM ": trade(brand)name, Kyoeisha Chemical Co., Ltd.'s system, (2-methacryloxyethyl) acid phosphoric acid ester.
Production Example 3
In above-mentioned Production Example 2, except monomer composition is 60 parts of 360 parts of methyl methacrylates, 200 parts of n-butyl acrylates, 250 parts of 2-Ethylhexyl Methacrylates, 130 parts of vinylformic acid 4-hydroxyl butyl esters, vinylformic acid, similarly carry out with above-mentioned Production Example 2, obtain water-soluble acrylic resin (B-2).
The manufacture > of < acrylic resin emulsion
Production Example 4
In reaction vessel, add 1 part in 100 parts of deionized waters, 2.5 parts of " Adelcuria soap SR-1025 " (trade(brand)name, rising sun electrification society system, reactive emulsifier, solids components 25%) and monomer mixture (9 parts of vinylbenzene, 40 parts of n-butyl acrylates, 40 parts of 2-EHAs, 10 parts of Hydroxyethyl acrylates, 1 part of methacrylic acid), in nitrogen gas stream, be uniformly mixed, at 60 ℃, add 3 parts of 3% ammonium persulphates.Then, be warming up to 80 ℃, use pump of constant delivery type, spend 4 hours the pre-emulsion (Pre-emulsion) of 100 parts of all the other 99 parts of comprising above-mentioned monomer mixture, " Adelcuria soap SR-1025 " 2.5 parts, 4 parts of 3% ammonium persulphates and deionized waters is joined in reaction vessel, after interpolation finishes, carry out slaking in 1 hour.Then, add 33 parts of deionized waters, with dimethylethanolamine, be adjusted to pH7.5, obtain the acrylic resin emulsion (C-1) of median size 0.1 μ m, solid component concentration 30%.
Production Example 5
In reaction vessel, add 300 parts of deionized waters, " Adelcuria soap SR-1025 " 8 parts, after nitrogen displacement, make it be warming up to 85 ℃.Add wherein by 0.8 part of ammonium persulphate and following (A) and form 3.5% of pre-emulsion that emulsification forms, add after 20 minutes, spend the rest part that drips above-mentioned pre-emulsion for 170 minutes.
< core composition (A) >
Figure BDA0000447731050000261
Figure BDA0000447731050000271
Drip and finish post curing 1 hour, then spend 70 minutes and drip to form by following (B) pre-emulsion that emulsification forms.
< shell component (B) >
Figure BDA0000447731050000272
After dropping finishes, through 30 minutes, spend dropping in 30 minutes to be dissolved in 16 parts of solution that form of deionized water by 0.8 part of ammonium persulphate, then keep 2 hours at 85 ℃.Then, temperature is reduced to below 40 ℃, with ammoniacal liquor, is adjusted to pH7～8, obtain the acrylic copolymer emulsion (C-2) of solid component concentration 47.6%.
The manufacture > of < aluminium pigment paste composition
Production Example 6
3 parts of the resin solutions (note 2) to adding 48.1 parts of aluminium pigment paste " WJE-7640 " (Toyoalumi society system, metal content 52%), 35 parts of ethylene glycol monobutyl ether and phosphorous acidic group in container, mix, and obtain aluminium pigment paste composition.
The resin solution of (note 2) phosphorous acidic group: comprise 27.5 parts of methoxypropanol to adding in reaction vessel, and the solvent of 27.5 parts of isopropylcarbinols, be heated to 110 ℃, then, spend 4 hours and will comprise 25 parts of vinylbenzene, 27.5 parts of n-BMAs, " vinylformic acid iso stearyl ester " (Osaka organic chemistry society system, trade(brand)name) 20 parts, 7.5 parts of vinylformic acid hydroxy butyl esters, 15 parts of the polymerizable monomers of phosphorous acidic group (note 3), 12.5 parts of 2-methacryloxyethyl acid phosphoric acid esters, 10 parts of isopropylcarbinols, and 121.5 parts, the mixture of 4 parts of tert-butyl hydroperoxide octanoates adds in above-mentioned solvent, then, spend and within 1 hour, drip the mixture comprise 20 parts of 0.5 part of tert-butyl hydroperoxide octanoate and Virahols, then, while stirring slaking 1 hour, obtain the resin solution of the phosphorous acidic group of solid component concentration 50%.
The polymerizable monomer of (note 3) phosphorous acidic group: to adding 41.1 parts of 57.5 parts of monobutyl phosphoric acid and isopropylcarbinols in reaction vessel, under the condition of blowing air, drip 42.5 parts of glycidyl methacrylate with 2 hours, then, while stir slaking 1 hour.Then, add 5.9 parts of Virahols, obtain the polymerizable monomer solution of the phosphorous acidic group of solid component concentration 50%.
The manufacture > > of < < host composition
Production Example 7
36.4 parts of the water-soluble acrylic resin solutions (B-1) obtaining in 86.1 parts of the aluminium pigment paste compositions obtaining in Production Example 6 and Production Example 2 are joined and are uniformly mixed in container, stir after 1 hour, mix 66.7 parts of 200 parts of ester-polyurethane resin emulsions (A-1) that obtain in Production Example 1 and the acrylic resin emulsion (C-1) obtaining in Production Example 4, the ratio that is 3.0 mass parts with respect to resin solid composition 100 mass parts according to the amount of effective constituent is added " Primal ASE60 " (note 4), then continues to stir 1 hour.The mixture obtaining is adjusted to after pH8.0 with dimethylethanolamine, adds deionized water, obtain the host (I-1) of solid component concentration 30%.The viscosity of this host (I-1) is 1000mPasec.
(note 4) " Primal ASE-60 ": trade(brand)name, Rohm and Haas society system, poly-(methyl) acrylic acid series viscous regulator, acid number 270mgKOH/g, effective constituent 28%.
Production Example 8
In above-mentioned Production Example 7, except water-soluble acrylic resin solution (B-1) being replaced to full dose water-soluble acrylic resin solution (B-2), all the other and above-mentioned Production Example 7 are similarly carried out, and obtain the host (I-2) of solid component concentration 30%.The viscosity of this host (I-2) is 1000mPasec.
Production Example 9(comparative example is used)
In above-mentioned Production Example 7, except being 5.5 mass parts according to making the use level of the effective constituent of " Primal ASE60 " (note 4) with respect to resin solid composition 100 mass parts, all the other and above-mentioned Production Example 7 are similarly carried out, and obtain host (I-3).The viscosity of host (I-3) is 3000mPasec.
Production Example 10(comparative example is used)
63.6 parts of the water-soluble acrylic resin solutions (B-1) obtaining in 86.1 parts of the aluminium pigment paste compositions obtaining in Production Example 6 and Production Example 2 are joined and are uniformly mixed in container, stir after 1 hour, by 100 parts of the ester-polyurethane resin emulsions obtaining in Production Example 1 (A-1) and 63.6 parts of mixing of acrylic resin emulsion (C-1) of obtaining in Production Example 4, add 12.5 parts of " Primal ASE60 " (notes 4), then continue to stir 1 hour.The mixture obtaining is adjusted to after pH8.0 with dimethylethanolamine, adds deionized water, obtain the host (I-4) of solid component concentration 30%.The viscosity of this host (I-4) is 1300mPasec.
The manufacture > > of < < viscous regulator composition (II)
Production Example 11
50.4 parts of the acrylic resin emulsions (C-2) obtaining in 109.1 parts of the water-soluble acrylic resin solutions (B-1) obtaining in Production Example 2 and Production Example 5 are joined and are uniformly mixed in container, stir after 1 hour, add 57.1 parts of " Primal ASE60 " (notes 4), then continue to stir 1 hour.The mixture obtaining is adjusted to after pH8.0 with dimethylethanolamine, adds deionized water, obtain the viscous regulator composition (II-1) of solid component concentration 10%.The viscosity of this viscous regulator composition (II-1) is 1000mPasec.
Production Example 12
In above-mentioned Production Example 11, except the condition full dose that is equivalent by acrylic resin emulsion (C-2) according to solids component replaces with water-soluble acrylic resin solution (B-1), all the other and above-mentioned Production Example 11 are similarly carried out, and obtain solid component concentration and be 10% viscous regulator composition (II-2).The viscosity of this viscous regulator composition (II-2) is 500mPasec.
Production Example 13
In above-mentioned Production Example 11, except making the solids component mass ratio of water-soluble acrylic resin solution (B-1) and acrylic resin emulsion (C-2), be 50/50, all the other and above-mentioned Production Example 11 are similarly carried out, and obtain solid component concentration and be 10% viscous regulator composition (II-3).The viscosity of this viscous regulator composition (II-3) is 1500mPasec.
Production Example 14
In above-mentioned Production Example 11, except the condition full dose that is equivalent by water-soluble acrylic resin (B-1) according to solids component replaces with acrylic resin emulsion (C-2), all the other and above-mentioned Production Example 11 are similarly carried out, and obtain solid component concentration and be 10% viscous regulator composition (II-X).The viscosity of this viscous regulator composition (II-X) is 2000mPasec.
Production Example 15(comparative example is used)
In 942.9 parts of deionized waters, add 57.1 parts of " Primal ASE60 " (notes 4), with dimethylethanolamine, be adjusted to pH8.0, obtain viscous regulator composition (II-5).The viscosity of viscous regulator composition (II-4) is high, is 4500mPasec.
Production Example 16(comparative example is used)
In above-mentioned Production Example 12, except the condition full dose that is equivalent by water-soluble acrylic resin solution (B-1) according to solids component replaces with ester-polyurethane resin emulsion (A-1), all the other and Production Example 12 are similarly carried out, and obtain solid component concentration and be 10% viscous regulator composition (II-6).The viscosity of this viscous regulator composition (II-5) is 2500mPasec.
The manufacture > > of < < viscous regulator composition (III)
Production Example 17
To being uniformly mixed in container, add 995 parts of deionized waters, 5 parts of " Laponite RD " (notes 5), be uniformly mixed, obtain viscous regulator composition (III-1).The viscosity of this viscous regulator composition (III-1) is 10mPasec.
(note 5) " Laponite RD "; Trade(brand)name, Wilbur-Ellis Co., Ltd., layered silicate synthesis, effective constituent 100%
Production Example 18
To being uniformly mixed in container, add 695 parts of deionized waters, 300 parts of ester-polyurethane resin emulsions (A-1), 5 parts of " Laponite RD " (notes 5), be uniformly mixed, obtain viscous regulator composition (III-2).The viscosity of this viscous regulator composition (III-2) is 300mPasec.
Production Example 19
To being uniformly mixed in container, add 965 parts of deionized waters, 30 parts, barium sulfate, 5 parts of " LaponiteRD " (notes 5), be uniformly mixed, obtain viscous regulator composition (III-3).The viscosity of this viscous regulator composition (III-3) is 30mPasec.
Production Example 20
To being uniformly mixed in container, add 665 parts of deionized waters, 30 parts, barium sulfate, 300 parts of ester-polyurethane resin emulsions (A-1), 5 parts of " Laponite RD " (notes 5), be uniformly mixed, obtain viscous regulator composition (III-4).The viscosity of this viscous regulator composition (III-4) is 350mPasec.
Production Example 21
To being uniformly mixed, in container, add 665 parts of deionized waters, 30 parts, barium sulfate, 300 parts of ester-polyurethane resin emulsions (A-1), 5 parts of " Laponite RD " (notes 5), 10 parts of " UNIOL D-2000 " (polypropylene glycols that trade(brand)name, NOF Corp's system, weight-average molecular weight are 2000), be uniformly mixed, obtain viscous regulator composition (III-5).The viscosity of this viscous regulator composition (III-5) is 340mPasec.
The manufacture > > of < < aqueous basecoat coating composition
Embodiment 1
70 parts of the hosts obtaining in above-mentioned Production Example (I-1) are uniformly mixed with 30 parts of viscous regulator compositions (II-1), add deionized water, obtain the aqueous basecoat coating composition (X-1) of solid component concentration 18.5%.
Embodiment 2～19 and comparative example 1～7
In above-described embodiment 1, except make the kind of host, viscous regulator composition and usage ratio as described in Table 1, all the other and above-described embodiment 1 similarly carry out, and obtain the aqueous basecoat coating composition (X-2) of solids component 18.5%～(X-26).
Comparative example 8
The aqueous basecoat coating composition (X-12) obtaining in above-described embodiment 12 is preserved 1 week at 25 ℃, using it as aqueous basecoat coating composition (X-27).
Be explained, the numerical value of each composition containing in the host of table 1 (I), viscous regulator composition (II), viscous regulator composition (III) is the amount of each composition contained in the aqueous basecoat coating composition that represents finally to obtain with solids component (effective constituent) ratio, and this is readily appreciated that.
Figure BDA0000447731050000321
Figure BDA0000447731050000331
Figure BDA0000447731050000341
Performance evaluation
By each aqueous basecoat coating composition obtaining in embodiment and comparative example for following performance evaluation.The results are shown in table 1.
(*) viscosity of aqueous basecoat coating composition
Use Brookfield type viscometer, at 25 ℃, with 60rpm, measure each aqueous basecoat coating composition obtained above.Be explained, measurement operation is carried out after each aqueous basecoat coating is manufactured latter 5 minutes.
(*) Combination
Each host (I), viscous regulator composition (II) and viscous regulator composition (III) are uniformly mixed after 1 minute with hand, by following benchmark evaluation coating state.
◎: each composition evenly mixes;
*: each composition mixes inhomogeneous, can observe the inhomogeneous point of part.
(*) resistance to flow
11 * 45cm size be coated with body of a motor car with the coated plate of varnish colour composition in the end with its long side the part apart from 3cm, take 2cm interval arranges the punching that 21 diameters of a row are 5mm, using this coated plate as coated article, under 25 ℃, the condition of relative humidity 40% according to form the mode of film thickness gradient at long side direction, each aqueous basecoat coating composition of application, this coated plate is generally perpendicularly being stood and placed, according to the temperature of coated plate, remain on the state of 60 ℃ by its forced drying 20 minutes, obtain the test coated plate of resistance to flow test use.Investigation respectively tests what obtain the position that 2mm place, distance punching bottom on coated plate observes coating flowing hanging, by measuring the thickness (sagging gauge thickness (μ m)) of this position, evaluates resistance to flow.Sagging gauge thickness is larger, represents that resistance to flow is better.
◎: sagging gauge thickness is more than 30 μ m;
〇: sagging gauge thickness is more than 20 μ m and be less than 30 μ m;
△: sagging gauge thickness is more than 10 μ m and be less than 20 μ m;
*; Sagging gauge thickness is less than 10 μ m.
(*) finished appearance (aluminum oxide orientation)
By being coated with coated plate for #800 wet-strong paper grinding, the degreasing of body of a motor car with varnish colour, make coated article.By this coated article horizontal positioned, under 25 ℃, the condition of relative humidity 40%, even each aqueous basecoat coating composition of spray-coating.Then adopt immediately spray-coating method to repeat to be coated with identical aqueous basecoat coating composition, then, adopt again immediately the identical aqueous basecoat coating composition of the 3rd application of spray-coating method, and, adopt again immediately the identical aqueous basecoat coating composition of spray-coating method the 4th application.Each application all carried out under 25 ℃, the condition of relative humidity 40%, between application and application, there is no interval, do not arrange blow or solidify, preheating procedure.That is, wet and cover wet continuous application.After the 4th application finishes, adopt air-jet method, carry out normal temperature and blow 10 minutes, make undercoat dried coating film, the undercoat that obtains dry film thickness 15 μ m is filmed.Then, as top layer varnish precision work, before facing application, " RETAN PG MULTCLEAR HX(Q) " (trade(brand)name, Northwest coating society system, the varnish colour of the acrylic resin that contains hydroxyl) be mixed into " RETANPG MULTCLEAR Standard solidifying agent " (trade(brand)name in 100 parts, Northwest coating society system, the isocyanuric acid ester type polyisocyanate curing agent of hexamethylene diisocyanate) 50 parts, obtain top layer varnish colour, then according to making the film dry film thickness of upper formation of undercoat become the condition of 40 μ m, the top layer varnish colour forming is like this carried out to air-jet method application, use drying machine that the temperature of coated plate is remained on to 60 ℃, forced drying in this state 20 minutes, the coated surface that visual valuation obtains.
◎: aluminum oxide pigment is parallel and even orientation with respect to painting face, does not observe the generation of metal speckle completely;
Zero: although aluminum oxide pigment with respect to painting face parallel and even orientation, observe and produce slight metal speckle;
△: aluminum oxide pigment is parallel but be not even orientation with respect to painting face, observes and produces a large amount of metal speckles;
*: aluminum oxide pigment is parallel but be not even orientation with respect to painting face, and observes the very a large amount of metal speckle of generation.
(*) covering property
The test that above-mentioned finished appearance is evaluated, except coated article being made to black and white screening rate test pater, the continuous application that all the other similarly carry out aqueous basecoat coating composition, obtains undercoat and films.By the black and white to the substrate of the coated plate obtaining, differentiate complexity and evaluate covering property.
◎: covering property is very good;
〇: covering property is good;
△: covering property is bad a little;
*: covering property is bad.
(*) tack
Respectively testing on coated plate of obtaining in above-mentioned finished appearance evaluation drawn to reaching base substrate with graduating with cutter, and 100 of the checkers of making 1mm * 1mm size, stick adhesive tape in its surface, investigate the residual number of filming at 20 ℃ of checkers of peeling off fast after this adhesive tape.
◎: residual 100;
Zero: residual 99～90;
△: residual 89～41;
*: residual below 40.
(*) water tolerance
Each test board obtaining in above-mentioned finished appearance evaluation is flooded 10 days in the warm water of 40 ℃, pull each film coated surface of rear observation out.
◎: very good;
Zero: good;
△: observe the slight abnormality such as expansion, albefaction;
*: observe expansion, albefaction etc. significantly abnormal.

Claims (8)

1. the water-based pigmented basecoat coating composition that multicomponent is, it is combined by host composition (I) and viscous regulator composition (II),
Host composition (I) contains water reducible resin composition (A), pigment (B), poly-(methyl) acrylic acid series viscous regulator (C) and water, and water reducible resin composition (A) contains by water-dilutable urethane resins more than solid component meter 30 quality % the part as this composition in composition (A) solids component; The amount of the effective constituent of poly-(methyl) acrylic acid series viscous regulator (C) is with respect to the solids component of water reducible resin composition (A) in the scope in 0.01～5.0 quality %;
Viscous regulator composition (II) contains water reducible resin composition (D), poly-(methyl) acrylic acid series viscous regulator (E) and water, and water reducible resin composition (D) contains by water-dilutable acrylic resins (d1) more than solid component meter 50 quality % the part as this composition in (D) composition solids component.
2. the water-based pigmented basecoat coating composition that multicomponent claimed in claim 1 is, wherein, water reducible resin composition (A) in host composition (I), except water-dilutable urethane resin, also contains water-soluble acrylic resin and acrylic resin emulsion.
3. the water-based pigmented basecoat coating composition that the multicomponent described in claim 1 or 2 is, wherein, the mass ratio of host composition (I) and viscous regulator composition (II), take that they add up to 100 mass parts as benchmark, in the scope of composition (I) in 40～95 mass parts, in the scope of composition (II) in 5～60 mass parts.
4. the water-based pigmented basecoat coating composition of the system of the multicomponent described in wantonly 1 of claim 1～3, wherein, the multicomponent system that it forms for also combine viscous regulator composition (III) except host composition (I) and viscous regulator composition (II), it is viscous regulator (F) and water that this viscous regulator composition (III) contains inorganic.
5. the water-based pigmented basecoat coating composition that multicomponent claimed in claim 4 is, wherein, viscous regulator composition (III) also contains water reducible resin composition (G).
6. the water-based pigmented basecoat coating composition that multicomponent claimed in claim 5 is, wherein, the water reducible resin composition (G) in viscous regulator composition (III) contains water-dilutable urethane resin as a part for this composition.
7. the water-based pigmented basecoat coating composition of the system of the multicomponent described in wantonly 1 of claim 4～6, wherein, viscous regulator composition (III) also contains pigment.
8. the water-based pigmented basecoat coating composition of the system of the multicomponent described in wantonly 1 of claim 4～7, wherein, the mass ratio of host composition (I), viscous regulator composition (II) and viscous regulator composition (III), take that they add up to 100 mass parts as benchmark, in the scope of composition (I) in 30～80 mass parts, in the scope of composition (II) in 1～40 mass parts, in the scope of composition (III) in 0.5～50 mass parts.
CN201280031818.9A 2011-06-30 2012-06-21 Multicomponent water-based colored base-coat paint composition Pending CN103649247A (en)

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