CN105792947B - Method of forming layered coating film - Google Patents

Method of forming layered coating film Download PDF

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Publication number
CN105792947B
CN105792947B CN201480064924.6A CN201480064924A CN105792947B CN 105792947 B CN105792947 B CN 105792947B CN 201480064924 A CN201480064924 A CN 201480064924A CN 105792947 B CN105792947 B CN 105792947B
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hydroxyl
resin
acid
mass
methyl
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CN105792947A (en
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古泽智
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Kansai Paint Co Ltd
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Kansai Paint Co Ltd
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    • 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
    • C08G18/4263—Polycondensates having carboxylic or carbonic ester groups in the main chain containing carboxylic acid groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/56—Three layers or more
    • B05D7/57—Three layers or more the last layer being a clear coat
    • B05D7/572—Three layers or more the last layer being a clear coat all layers being cured or baked together
    • 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
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    • 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
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/2815—Monohydroxy compounds
    • C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
    • C08G18/6225—Polymers of esters of acrylic or methacrylic acid
    • C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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
    • C08G18/703—Isocyanates or isothiocyanates transformed in a latent form by physical means
    • C08G18/705—Dispersions of isocyanates or isothiocyanates in a liquid medium
    • C08G18/706—Dispersions of isocyanates or isothiocyanates in a liquid medium the liquid medium being water
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    • 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
    • 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
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • 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
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/8093—Compounds containing active methylene groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2401/00—Form of the coating product, e.g. solution, water dispersion, powders or the like
    • B05D2401/20—Aqueous dispersion or solution
    • 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
    • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • 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
    • C09D169/00—Coating compositions based on polycarbonates; Coating compositions based on derivatives of polycarbonates
    • 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
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    • 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives

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

Abstract

The present invention provides a kind of method of forming layered coating film for carrying out following process successively：Specific aqueous 1st pigmented finiss (X) of application, aqueous 2nd pigmented finiss (Y) and clear dope (Z) on the coated article containing metal material and plastic material；And this 3 films is made to cure simultaneously, which is characterized in that aqueous 1st pigmented finiss (X) of application simultaneously makes thickness obtained from its curing be that average transmittance of 5 μm of the cured coating film at wavelength 360nm~420nm is less than 1%.

Description

Method of forming layered coating film
Technical field
(cross reference of association area)
This application claims the Japanese Patent Application 2013-255844 specifications submitted on December 11st, 2013, (it is integrally logical Cross and be incorporated herein by reference) priority interests.
No matter the present invention relates to a kind of formed compared with metal parts or plastic components is respectively provided with excellent resistance to burst apart Property, adhesion, retouching property, weatherability and ethanol petrol resistant film method of forming layered coating film.
Background technology
In general, car body, which has, forms the plastic components such as metal parts and the bumper of vehicle body.
In the application of the car body, previous widely used following process：Using suitable for metal parts and plastic components The different coating and different coating process for waiting all parts carry out application, then, plastic components are installed on metal parts.
But in recent years, the equipment cost in the manufacturing process of car body and metal parts and plastics are made to reduce The tone of component is consistent, seeks a kind of method of the application in a state that plastic components to be installed on to metal parts.
Such as a kind of body of a motor car for having acrylic resin component in metal foil over-assemble is disclosed in patent document 1 Coating process.
But the middle painting coating disclosed in patent document 1 does not have electric conductivity, it is therefore necessary to which polypropylene member application is led Electrical primer base.In other words, in patent document 1, polypropylene member successively application conductive primers coating → middle painting is applied Material → painting coating, to applying coating → painting coating in metal parts successively application.That is, due to being not by plastic section Part and metal parts carry out application all of identical coating and identical coating process, therefore in cost reduction and tone one The aspect of cause is insufficient.
One kind is disclosed in patent document 2 contains specific anionic property urethane resin emulsion and specific urethane resin Water-based paint compositions.But by the paint spraying in the case of metal parts and plastic components, even if chipping resistance It has no problem with light transmittance, can not affirm that the adhesion for plastic components compared with waterborne conductive priming paint is abundant.
There is one kind to contain water polyolefin system resin (A), selected from aqueous poly- with specific ratio disclosed in patent document 3 At least one kind of water-base resin (B), polyester resin (C) and crosslinking agent (D) in urethane resin and water-based acrylic resin Water-borne primer coating composition.But by the paint spraying in the case of metal parts and plastic components, even if compared with The adhesion of plastic components has no problem, it is also difficult to say that chipping resistance and light transmittance are abundant compared with aqueous middle painting coating.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2012-213692 publications
Patent document 2：Japanese Unexamined Patent Publication 2005-330339 publications
Patent document 3：WO2007/66827 publications
The content of the invention
The subject that the invention solves
The present invention considers above-mentioned aspect and makes, can be formed compared with metal parts its purpose is to provide one kind and The multilayer that plastic components has the film of excellent chipping resistance, adhesion, retouching property, weatherability and ethanol petrol resistant applies Film forming method.
Means needed for solving the problems, such as
The present inventor is concentrated on studies to achieve these goals, it turns out that passing through a kind of multilayer film side of being formed Method can solve the above subject, so as to complete the present invention, the use on coated article successively aqueous 1st pigmented finiss of application, In the method for forming layered coating film of 3 applications, 1 roasting mode of aqueous 2nd pigmented finiss and clear dope, using containing Chlorine-free polyolefin-based resins (A), specific waterborne polyurethane resin (B), the sealing end with nonionic hydrophilic radical gather different The coating of cyanate esters (C) and conductive pigment (D) is as aqueous 1st pigmented finiss (X), which is characterized in that application Aqueous 1st pigmented finiss (X) and make its cure obtained from thickness be 5 μm of cured coating film at wavelength 360nm~420nm Average transmittance be less than 1%.
That is, the present invention provides following method of forming layered coating film.
Item 1.
A kind of method of forming layered coating film, to carry out the method for forming layered coating film of following process successively：
(1) on the coated article containing metal material and plastic material aqueous 1st pigmented finiss (X) of application and formed solid The process for the 1st coloring film changed；
(2) obtained by process (1) it is uncured 1st coloring film on aqueous 2nd pigmented finiss (Y) of application and shape Into the process of the uncured 2nd coloring film；
(3) transparent paint coating (Z) is not solid to be formed on the uncured 2nd coloring film obtained by process (2) The process of the transparent coating of change；And
(4) by colouring film, uncured 2nd coloring painting to the uncured 1st formed in process (1)~(3) Film and uncured transparent coating are heated and make this 3 films cured process simultaneously, which is characterized in that
Above-mentioned aqueous 1st pigmented finiss (X) containing chlorine-free polyolefin-based resins (A), acid value be 1mgKOH/g~ The waterborne polyurethane resin that 30mgKOH/g and the time at a temperature of 20 DEG C until film forming are 5 minutes~20 minutes (B), there is the blocked polyisocyanate compound (C) of nonionic hydrophilic radical and conductive pigment (D),
Above-mentioned aqueous 1st pigmented finiss (X) of application and make its cure obtained from thickness be 5 μm of cured coating film in wavelength Average transmittance at 360nm~420nm is less than 1%.
Invention effect
By the method for forming layered coating film of the present invention, no matter can also be formed compared with metal parts even if without using priming paint Or it is respectively provided with excellent chipping resistance, adhesion, retouching property, weatherability and ethanol petrol resistant compared with plastic components Film.
Specific embodiment
Hereinafter, the method for forming layered coating film of the present invention is illustrated in further detail.
In the present specification, the feelings except there is a situation where in addition to express in the present specification or in the clear and definite contradiction of context Outside condition, singulative includes single and multiple.
Process (1)
In the process (1) of the present invention, aqueous 1st coloring of application on the coated article containing metal material and plastic material Coating (X).Aqueous 1st pigmented finiss (X) is especially coated on metal material and plastic material.As coated article, without special It limits, for example,：The automobile exterior panels such as passenger car, truck, motorcycle, bus portion；The auto parts such as bumper；It moves Outer plate portion of the home electrics articles for use such as mobile phone, stereo set etc..
As metal parts, for example,：Iron, aluminium, brass, copper, tinplate, stainless steel, galvanized steel and zinc-plated Steel of alloy (Zn-Al, Zn-Ni, Zn-Fe etc.) etc..
Above-mentioned metal parts can also be that its surface is implemented at phosphate treated, chromic acid salt treatment and composite oxides The metal parts of the surface treatments such as reason, and then can also be the metal parts for being formed on primary coat film, primary coat film profit It is formed with bottom-coating.As bottom-coating, it can be cited for example that electrocoating paint, wherein, preferred cationic electro-deposition applies Material.
As the material of plastic components, such as particularly preferably make the carbon numbers such as ethylene, propylene, butylene, hexene 2~10 1 kind of olefines or the polyolefin that forms of two or more (co) polymerization, in addition, can also enumerate：Makrolon, ABS Resin, urethane resin, polyamide etc..As these plastic components, for example,：Bumper, spoiler, grid, gear mud The automobile exterior panels such as plate portion；Outer plate portion of home electric articles for use etc..These plastic components can be aqueous 1st of the application present invention the By method known per se suitable for progress ungrease treatment, washing process etc. before color coating (X).
Above-mentioned metal parts and plastic components can be assembled by known method.
Aqueous 1st pigmented finiss (X)
As aqueous 1st pigmented finiss (X) of institute's application on the coated article containing above-mentioned metal material and plastic material, Gather containing chlorine-free polyolefin-based resins (A), specific waterborne polyurethane resin (B), the sealing end with non-aqueous hydrophilic radical Isocyanate compound (C) and conductive pigment (D).
In addition, aqueous 1st pigmented finiss (X) of application and make its cure obtained from thickness be 5 μm of cured coating film in ripple Average transmittance at long 360nm~420nm is less than 1%.
Chlorine-free polyolefin-based resins (A)
Chlorine-free polyolefin-based resins (A) import the hydrophilies such as carboxyl using molecular polyolefin as main framing and in the molecule thereof Group forms, it is usually preferred to unsaturated carboxylic acid or anhydride modified polyolefin (a).
Unsaturated carboxylic acid or anhydride modified polyolefin (a) can usually be made by method known per se unsaturated carboxylic acid or Person's acid anhydrides is obtained with polyolefin graft copolymerization.As available for modified unsaturated carboxylic acid or acid anhydrides, carbon number is included For 3~10 aliphatic carboxylic acid or its acid anhydride, wherein, the aliphatic carboxylic acid or its acid anhydride in 1 molecule containing at least one, preferably 1 Polymeric double bond and not chloride, specifically, for example,：(methyl) acrylic acid, maleic acid, fumaric acid, itaconic acid, horse Carry out acid anhydrides etc., wherein, particularly preferred maleic acid and maleic anhydride.Compared with the utilization of the polyolefin unsaturated carboxylic acid or its acid The graft copolymerization amount of acid anhydride can change according to desired physical property of improved polyalkene etc., but usually with the solid constituent of polyolefin Be the weight % of 0.5 weight %~4 on the basis of weight, be preferably the weight % of 1 weight %~3, further preferably 1.2 weight %~ In the range of 2.8 weight %.
On the other hand, for modified polyolefin carbon number such as comprising ethylene, propylene, butylene, hexene is made for 2~ The polyolefin not being chlorinated that a kind of 10 alkene or two or more (co) polymerization form particularly preferably contain propylene as gathering Close the polyolefin of unit.The weight fraction of propylene units in improved polyalkene is from the intermiscibility with other ingredients and forms film The viewpoints such as adhesion consider, be typically 0.5~1, particularly preferably 0.7~0.99, further particularly preferably 0.8~0.99 In the range of.
As said polyolefins, can without particular limitation using the polyolefin known per se not being chlorinated, but from From the aspect of the narrow molecular weight distribution of obtained polyolefin and random copolymerization etc. are also excellent, it is preferable to use single site catalysts As polymerization catalyst and the polyolefin by the way that alkene (co) polymerization is manufactured.Single site catalysts are active site even structures The polymerization catalyst of (unit point), in the single site catalysts, particularly preferred metallocene series catalysts.The metallocene series catalysts Being used as at least tool by combination, there are one conjugation IVB~group vib of the periodic table of elements of five-membered ring ligand or the transition of VIII group The metallocene of metallic compound or the terres rares transistion metal compound of IIIB races (double (cyclopentadienyl group) metal complexes and its Derivative), it is prepared by the organo-aluminum compounds such as co-catalysts and trimethyl aluminium such as the aikyiaiurnirsoxan beta that is activated or boron system.Alkene (co) polymerization can be supplied to according to method known per se, alkene and hydrogen such as by one side by propylene or ethylene reaction hold The method of alkyl aluminum and Metallocene-type catalysts is continuously added in device on one side and is carried out.
Above-mentioned unsaturated carboxylic acid or anhydride modified polyolefin (a) can also further carry out acrylic acid modified.As The acrylic acid series unsaturated monomer acrylic acid modified available for this, can enumerate not chloride acrylic acid series unsaturated monomer, example Such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) cyclohexyl acrylate, (methyl) 2-EHA, (methyl) lauryl acrylate, (first Base) (methyl) acrylic acid such as stearyl acrylate base ester C1~C20 Arrcostabs；(methyl) acrylic acid 2- hydroxy methacrylates, (methyl) C1~C21 hydroxyalkyl acrylates of acrylic acid 3- hydroxy propyl esters etc. (methyl) acrylic acid；(methyl) acrylic acid, the contracting of (methyl) acrylic acid The others acrylic monomer such as water glyceride, (methyl) acrylamide, (methyl) acrylonitrile further enumerates styrene etc., These can individually using or two or more is applied in combination.
In addition, in the present specification, " (methyl) acrylic acid " refers to " acrylic or methacrylic acid ", " (methyl) propylene Acid esters " refers to " acrylate or methacrylate ".
The acrylic acid modified of said polyolefins can for example be carried out by operating as follows：First, make for manufacturing as described above Unsaturated carboxylic acid or anhydride modified polyolefin in carboxyl have reactivity not chloride acrylic acid series unsaturated monomer, Such as (methyl) glycidyl acrylate etc. reacts and imports polymerism unsaturated group to polyolefin, then, makes above-mentioned third Olefin(e) acid system unsaturated monomer alone or in combination two or more be imported with this polymerism unsaturated group polyolefin it is (common) poly- It closes.Polyolefin it is acrylic acid modified in the usage amount of aforesaid propylene acids unsaturated monomer can be according to desired by improved polyalkene Physical property etc. and change, but from the intermiscibility with other ingredients and the adhesion for forming film etc. consideration, usually with It is preferably below 30 weight % on the basis of the unsaturated carboxylic acid or the solids by weight of anhydride modified polyolefin (a) that arrive, it is special Not You Xuanwei the weight % of 0.1 weight %~20, further particularly preferably in the range of the weight % of 0.15 weight %~15.
Above-mentioned unsaturated carboxylic acid or anhydride modified polyolefin (a) can also further use the chemical combination with polyoxyalkylene chain Object is modified.As the polyoxyalkylene chain in the compound with polyoxyalkylene chain, for example,：Polyoxyethylene chain, Block chain of polyoxypropylene chains, polyoxyethylene and polyoxypropylene etc..
The above-mentioned compound with the polyoxyalkylene chain generally preferably scope with 400~3,000, preferably 500~2,000 Interior number-average molecular weight.If the number-average molecular weight is less than 400, the effect as hydrophilic radical can not be fully played, is had Harmful effect may be caused to water resistance, on the other hand, if the number-average molecular weight be more than 3,000, then cure at room temperature and Dissolubility is made to be deteriorated, it is possible to not easy to operate.
From with other ingredients intermiscibility, the interlayer that forms the adhesion of film and plastic components or film layer is applied with face it is attached Property etc. consideration it is expected the fusing point of above-mentioned unsaturated carboxylic acid or anhydride modified polyolefin (a) below 120 DEG C, preferably For 60 DEG C~110 DEG C, further preferably in the range of 70 DEG C~100 DEG C, and its weight average molecular weight (Mw) it is expected 10, In the range of 000~230,000, preferably in the range of 50,000~200,000, further preferably 60,000~150, In the range of 000.
In addition, apply the interlayer adhesion of film layer compared with the adhesion of plastic components or with face from formation film etc. Consider, it is usually desirable to which the melting caloric of above-mentioned unsaturated carboxylic acid or anhydride modified polyolefin (a) is 1mJ/mg~50mJ/mg's In the range of, it is especially desired in the range of 2mJ/mg~50mJ/mg.
Here, the fusing point and melting caloric of above-mentioned unsaturated carboxylic acid or anhydride modified polyolefin (a) can be by operating It arrives：Using Differential Scanning Calorimetry measuring device " DSC-5200 " (manufacture of Seiko Electronics Industry Company, trade name), using modified poly- Alkene 20mg is warming up to 150 DEG C with 10 DEG C/min of heating rate to measure heat from -100 DEG C.Above-mentioned unsaturated carboxylic acid or acid The fusing point of anhydride modified polyolefin (a) adjustment can by change polyolefin monomer composition, particularly 'alpha '-olefin monomers amount come It carries out.In addition, in the case where melting caloric is not easy to be obtained, 120 DEG C can be temporarily heated to by the way that sample will be measured, then with 10 After DEG C/min being cooled to room temperature, 2 days or more are stood, so as to measure heat.
In addition, the weight average molecular weight of above-mentioned unsaturated carboxylic acid or anhydride modified polyolefin (a) is will to utilize gel infiltration Value obtained from the weight average molecular weight that chromatography measures is converted on the basis of the weight average molecular weight of polystyrene, as gel infiltration color Spectrum uses " HLC/GPC150C " (Waters companies manufacture, 60cm × 1) and the o-dichlorohenzene as solvent, with 135 DEG C of column temperature, Flow 1.0ml/min is measured.Injection sample passes through using the solution concentration compared with o-dichlorohenzene 3.4ml as polyolefin 5mg Mode dissolve at 140 DEG C 1~3 it is small when prepare.In addition, as the column for gel permeation chromatography, can use " GMHHR-H (S) HT " (manufacture of Tosoh (strain) company, trade name).
And then above-mentioned unsaturated carboxylic acid or anhydride modified polyolefin (a) from the intermiscibility with other ingredients or form painting Adhesion of film etc. consideration, it is usually desirable to the model of the ratio between weight average molecular weight and number-average molecular weight (Mw/Mn) 1.5~7.0 In enclosing, preferably in the range of 1.8~6.0, further preferably in the range of 2.0~4.0.
Above-mentioned chlorine-free polyolefin-based resins (A) can be by by unsaturated carboxylic acid described above or anhydride modified polyene Hydrocarbon (a) is scattered to carry out moisture dispersion in an aqueous medium, usually can be by by unsaturated carboxylic acid or anhydride modified polyolefin (a) some or all of carboxyl in are neutralized with amine compounds and/or are dissipated using emulsifier to carry out moisture.From carrying From the aspect of high-dispersed, it is expected simultaneously using the moisture dispersion by neutralizing and emulsifier carries out.
As the amine compounds for neutralization, for example,：Triethylamine, tri-n-butylamine, dimethylethanolamine, three ethyl alcohol The tertiary amines such as amine；The secondary amine such as diethylamine, dibutyl amine, diethanol amine, morpholine；Primary amine such as propylamine, ethanolamine etc..Use these amine compounds Its usage amount during object is preferably with respect to the carboxyl in unsaturated carboxylic acid or anhydride modified polyolefin (a) usually at 0.1 mole In the range of the molar equivalent of equivalent~1.0.
As mentioned emulsifier, for example, polyoxyethylene list oleyl ether, polyoxyethylene list octadecyl ether, Polyoxyethylene list lauryl ether, polyoxyethylene tridecyl ether, polyoxyethylene phenyl ether, ethylene nonyl phenyl ether, polyoxy Ethylene octyl phenyl ether, Vinlub 73, polyoxyl 40 stearate, Aceonon 300 MO, dehydration mountain Pears alcohol monolaurate, sorbitan monostearate, sorbitan trioleate, polyoxyethylene sorbitan Dan Yue The anionic species such as the sodium salt or ammonium salt of the nonionics class emulsifier such as cinnamic acid ester, alkyl sulfonic acid, alkyl benzene sulphonate, alkyl phosphoric acid etc. breast Agent etc., and then, can also use has anionic group and the polyoxygenateds such as polyoxyethylene groups or polyoxypropylene base in 1 molecule There is the anionic group and polymerism insatiable hunger in alkenyl, anionic emulsifier or 1 molecule containing polyoxyalkylenes With the reactive anionic emulsifier of group etc..These emulsifiers can individually using or two or more is applied in combination.
Compared with 100 parts by weight of solid constituent of above-mentioned unsaturated carboxylic acid or anhydride modified polyolefin (a), above-mentioned breast Agent can usually use in the range of the parts by weight of 1 mass parts~20.
The emulsification method of above-mentioned unsaturated carboxylic acid or anhydride modified polyolefin (a) is not particularly limited, and example may be employed Such as Phase inversion emulsification, D phases emulsify, the emulsification of forced emulsification, gel, self-emulsifying, reversion emulsification, method known to high-pressure emulsification etc..Its In, from the viewpoint of the appearance and water resistance of obtained film, preferably by the method for self-emulsifying.
In addition, the unsaturated carboxylic acid or the aqueous dispersion of anhydride modified polyolefin (a) that as above obtain can also pass through By will be in acrylic acid modified explanation in the presence of the unsaturated carboxylic acid or anhydride modified polyolefin (a) that are water dispersible In the acrylic acid series unsaturated monomer listed carry out emulsion polymerization and be made and further contain through acrylic acid modified unsaturated carboxylic The chlorine-free polyolefin-based resins (A) of acid or anhydride modified polyolefin.
It is examined in terms of the chipping resistance of obtained film, adhesion, retouching property, weatherability and ethanol petrol resistant Consider, on the basis of total resin solid content quality in aqueous 1st pigmented finiss (X), above-mentioned chlorine-free polyolefin-based resins (A) Content be the mass % of 10 mass %~60, be preferably the mass % of 20 mass %~50, further preferably 25 mass %~50 Quality %.
Waterborne polyurethane resin (B)
Waterborne polyurethane resin (B) refers to using water as the aqueous medium of primary solvent or decentralized medium to divide Scattered polyurethane resin can be water-soluble type, colloidal dispersion type, emulsion types as the form of aqueous medium And any one of slurry types, but preferably colloidal dispersion type or emulsion types.
As above-mentioned waterborne polyurethane resin (B), waterborne polyurethane resin known per se can be used, preferably for example by Waterborne polyurethane resin obtained from following operation, i.e. in the presence of 1 molecules such as glycol, the diamines as chain elongation agent extremely Polyurethane is further optionally carried out to the obtained substance of chain elongation when there is the low molecular weight compound of 2 reactive hydrogens less, Steadily it can disperse in an aqueous medium or dissolve and use, the polyurethane is by making polyester polyol, polycarbonate polyol Obtained by the polyalcohols such as alcohol, polyether polyol or the reaction of the hydroxy-containing compounds and polyisocyanate of low molecular weight.
As above-mentioned polyol component, from the chipping resistance of obtained film, adhesion, retouching property, weatherability and resistance to From the aspect of ethanol vapor oiliness, particularly preferred polyester polyol and polyether polyol.
Above-mentioned polyester polyol used in manufacture as above-mentioned waterborne polyurethane resin (B), for example,： As obtained by reacting the aliphatic dicarboxylic acids such as the aliphatic diols such as 1,4- butanediols, 1,6-HD and adipic acid, decanedioic acid The polyester polyol arrived；It is more by the way that the aromatic dicarboxylic acids such as the aliphatic diol and terephthalic acid (TPA) is made to react obtained polyester First alcohol etc., as polycarbonate polyol, for example,：By making 1,6-HD, 3- methyl-1s, 5- pentanediols etc. two The carbonates such as alcohol and dimethyl carbonate react obtained polycarbonate polyol etc., as polyether polyol, such as can be with It enumerates：The ring-opening polymerisations such as ethylene oxide, propylene oxide by making polyethylene glycol, polypropylene glycol and polytetramethylene glycol etc. are obtained Polyalkylene glycol etc..In addition, as above-mentioned polyisocyanate, for example,：Hexamethylene diisocyanate, two hexamethylenes Aliphatic such as dicyclohexylmethane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate and alicyclic Diisocyanate and their isocyanurate ring addition product etc..As above-mentioned polisocyanate component, from obtained film Chipping resistance, adhesion, retouching property, from the aspect of weatherability and ethanol petrol resistant, particularly preferred isophorone two Isocyanates.
Moreover, for the glycol as chain elongation agent, for example,：Ethylene glycol, 1,4- butanediols, 1,5- penta 2 Alcohol, 3- methyl-1s, 5- pentanediols, cyclohexanediol etc., as diamines, for example,：Ethylenediamine, propane diamine, xyxylene Diamines etc..
As the method that above-mentioned waterborne polyurethane resin (B) is made steadily to disperse or dissolve in water, such as can make Use the following method.
(1) it is former as the manufacture of polyurethane by using the carboxylic glycol such as dihydromethyl propionic acid, dimethylolpropionic acid Material to introduce carboxyl to polyurethane, hydrophily is assigned to polyurethane by neutralizing part or all of the carboxyl, by certainly Emulsion dispersion is dissolved in the water.
(2) polyalcohol for manufacturing raw material as polyurethane uses the hydrophilic polyol as polyethylene glycol, manufacture Water-soluble polyurethane, is dispersed or dissolved in water.
(3) oxime, alcohol, phenol, mercaptan, amine, bisulfite are used to reacting the polyurethane finished or terminal isocyanate group The end-capping reagents such as sodium are blocked, and obtained polyurethane nonionic and/or cationic emulsifier and mechanical shear stress is strong System is dispersed in water.
(4) urethane prepolymer with terminal isocyanate group with water/emulsifier/chain elongation agent is mixed, uses mechanical shear Shear force is carried out at the same time scattered and molecular weight.
As above-mentioned waterborne polyurethane resin (B), the polyurethane obtained by single manufacturing method is not limited to, also may be used To use the mixture of the polyurethane obtained by various methods.
From the aspect of the chipping resistance of obtained film, adhesion, retouching property, weatherability and ethanol petrol resistant, The acid value of waterborne polyurethane resin (B) is in the range of 1mgKOH/g~30mgKOH/g, preferably in 3mgKOH/g~25mgKOH/ In the range of g, further preferably in the range of 5mgKOH/g~20mgKOH/g.
From the aspect of the chipping resistance of obtained film, adhesion, retouching property, weatherability and ethanol petrol resistant, on It is 5 minutes~20 minutes to state time of the waterborne polyurethane resin (B) at a temperature of 20 DEG C until film forming, is preferably 10 points Clock~20 minute, further preferably 12 minutes~18 minutes.
Here, the so-called time until film forming refers to that waterborne polyurethane resin forms the time needed for continuous film.Water Property polyurethane resin to film forming until time measure as follows.
Solid constituent is adjusted to under 20 DEG C of room temperature, 60% atmosphere of humidity using metering bar coater 28% aqueous poly- ammonia The coating of ester resin solution is on a pet film so that wet-film thickness is 40 μm.The starting point of time measurement, Mei Geyi will be set to after firm application 0.3mL ion exchange waters are added dropwise using dropper in the height of 1cm from film of fixing time, by the drop diameter after firm be added dropwise in 1 second Variation terminal is set in below 1mm, the time of origin-to-destination is set to " waterborne polyurethane resin is until film forming Time ".
From the aspect of the chipping resistance of obtained film, adhesion, retouching property, weatherability and ethanol petrol resistant, Preferably, the average grain diameter of above-mentioned waterborne polyurethane resin (B) aqueous medium is 70nm~250nm, preferably 80nm~ 230nm, further preferably 100nm~200nm.
In the present specification, average grain diameter is made by conventional method using dynamic light scattering method particle diameter distribution measuring device The value measured after being diluted with deionized water at 20 DEG C.As the dynamic light scattering method particle diameter distribution measuring device, such as can be with It uses " sub-micron grade particle analyzer N5 " (trade name, the manufacture of Beckman Coulter companies).
It is examined in terms of the chipping resistance of obtained film, adhesion, retouching property, weatherability and ethanol petrol resistant Consider, on the basis of the resin solid content quality total amount in aqueous 1st pigmented finiss (X), it is preferable that aqueous 1st pigmented finiss (X) content of the above-mentioned waterborne polyurethane resin (B) in is suitably for the mass % of 10 mass %~50, is preferably 10 mass %~40 Quality %, further preferably the mass % of 15 mass %~30.
Blocked polyisocyanate compound (C) with nonionic hydrophilic radical
Blocked polyisocyanate compound (C) with nonionic hydrophilic radical is with 2 or more in 1 molecule A part of isocyanate group of the polyisocyanate compounds of isocyanate group is by the modification of nonionic hydrophilic radical, remaining one All or part of isocyanate group is blocked the compound of agent sealing end.
Blocked polyisocyanate compound (C) with nonionic hydrophilic radical can be obtained by known method.Example Such as by the active hydrogen-contg compound (c2) and end-capping reagent (c3) for making there is nonionic hydrophilic radical with having in 1 molecule There is the reaction of the isocyanate group in the polyisocyanate compounds (c1) of 2 or more isocyanate group to obtain with nonionic The blocked polyisocyanate compound of hydrophilic radical (below, the sealing end with nonionic hydrophilic radical as above obtained is gathered Isocyanate compound is known as " (C1) ").
Isocyanate group in above-mentioned polyisocyanate compounds (c1) are made has nonionic hydrophilic radical with above-mentioned Active hydrogen-contg compound (c2) and end-capping reagent (c3) react in the case of, the polyisocyanate compounds (c1), have parent The active hydrogen-contg compound (c2) of water base group and the reaction sequence of end-capping reagent (c3) are not particularly limited.It specifically, can be with It enumerates：Make the active hydrogen-contg compound with hydrophilic radical (c2) and the isocyanate group in polyisocyanate compounds (c1) After part reaction, method that remaining isocyanate group is blocked with end-capping reagent (c3)；By polyisocyanate compounds (c1) In isocyanate group a part with end-capping reagent (c3) block after, make the active hydrogen-contg compound with hydrophilic radical (c2) with The method of remaining isocyanate group reaction；And make the active hydrogen-contg compound with hydrophilic radical (c2) and end-capping reagent (c3) Method reacted simultaneously with the isocyanate group in polyisocyanate compounds (c1) etc..
Polyisocyanate compounds (c1)
Polyisocyanate compounds (c1) are the compound at least with 2 isocyanate group in 1 molecule, such as can To enumerate：Aliphatic polymeric isocyanate, alicyclic polymeric isocyanate, aromatic-aliphatic polyisocyanate, aromatic series polyisocyanate The derivative etc. of ester, the polyisocyanate.
As above-mentioned aliphatic polymeric isocyanate, for example,：Trimethylene diisocyanate, tetramethylene two are different Cyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2- trimethylene diisocyanates, 1,2- butylidenes Diisocyanate, 2,3- tetramethylene diisocyanates, 1,3- tetramethylene diisocyanates, 2,4,4- 2,2,4- trimethyls six Methylene diisocyanate, dimer acid diisocyanate, 2,6- diisocyanates root close methyl caproate (trivial name：Lysine two is different Cyanate) etc. aliphatic diisocyanates；2,6- diisocyanates root closes caproic acid 2- isocyanato ethyls, 1,6- diisocyanate roots Conjunction -3- isocyanatomethyls hexane, tri- isocyanato- octanes of 1,4,8-, tri- isocyanato- hendecanes of 1,6,11-, 1,8- Diisocyanate root conjunction -4- diisocyanates root closes methyloctane, tri- isocyanato- hexanes of 1,3,6-, 2,5,7- trimethyls -1,8- Aliphatic triisocyanates such as diisocyanate root conjunction -5- isocyanatomethyl octanes etc..
As above-mentioned alicyclic polymeric isocyanate, for example,：1,3- cyclopentene diisocyanates, 1,4- hexamethylenes Diisocyanate, 1,3- cyclohexane diisocyanates, 3- isocyanatomethyl -3,5,5- trimethylcyclohexylisocyanates (trivial name：Isophorone diisocyanate), 4- methyl-1s, 3- cyclohexene diisocyanate (trivial names：Hydrogenate TDI), 2- first Double (isocyanatomethyl) hexamethylene (trivial names of base -1,3- cyclohexene diisocyanate, 1,3- or 1,4-：Hydrogenate diformazan Phenylene diisocyanate) or its mixture, di-2-ethylhexylphosphine oxide (4,1- hexamethylenes diyl) diisocyanate (trivial name：Hydrogenate MDI), The alicyclic diisocyanates such as norbornene alkyl diisocyanate；Tri- isocyanatocyclohexanes of 1,3,5-, 1,3,5- trimethyls are different Cyanate radical trimethylcyclohexane, 2- (3- isocyanatopropyls) -2,5- two (isocyanatomethyl)-bicyclic (2.2.1) heptane, 2- (3- isocyanatopropyls) -2,6- two (isocyanatomethyl)-bicyclic (2.2.1) heptane, 3- (3- isocyanato-s third Base) -2,5- two (isocyanatomethyl)-bicyclic (2.2.1) heptane, 5- (2- isocyanatoethyls) -2- isocyanato-s Methyl -3- (3- isocyanatopropyls)-bicyclic (2.2.1) heptane, 6- (2- isocyanatoethyls) -2- isocyanato- first Base -3- (3- isocyanatopropyls)-bicyclic (2.2.1) heptane, 5- (2- isocyanatoethyls) -2- isocyanato- first Base -2- (3- isocyanatopropyls)-bicyclic (2.2.1)-heptane, 6- (2- isocyanatoethyls) -2- isocyanato- first Alicyclic triisocyanates such as base -2- (3- isocyanatopropyls)-bicyclic (2.2.1) heptane etc..
As above-mentioned aromatic-aliphatic polyisocyanate, for example,：Di-2-ethylhexylphosphine oxide (4,1- phenylenes) two isocyanides Acid esters (trivial name：MDI), 1,3- or 1,4- xylene diisocyanate or its mixture, ω, ω '-diisocyanate root conjunction- Double (1- isocyanato- -1- Methylethyls) benzene (trivial names of 1,4- diethylbenzenes, 1,3- or 1,4-：Tetramethyl xylene two Isocyanates) or the araliphatic diisocyanates such as its mixture；The fragrance fat such as tri- isocyanatomethylbenzenes of 1,3,5- Fat race triisocyanate etc..
As above-mentioned aromatic poly-isocyanate, for example,：It is metaphenylene diisocyanate, different to phenylene two Cyanate, 4,4'- diphenyl diisocyanates, 1,5- naphthalene diisocyanates, 2,4 toluene diisocyanate (trivial name：2,4- ) or 2,6- toluene di-isocyanate(TDI) (trivial names TDI：2,6-TDI) or its mixture, 4,4'- toluidine diisocyanates, The aromatic diisocyanates such as 4,4'- diphenyl ether diisocyanates；Triphenyl methane -4,4', 4 "-triisocyanate, 1,3,5- The aromatic tri-isocyanates such as three isocyanato- benzene, tri- isocyanato- toluene of 2,4,6-；4,4'- diphenyl methane -2,2', Aromatic series tetraisocyanate such as 5,5'- tetraisocyanates etc..
In addition, the derivative as above-mentioned polyisocyanate, for example,：The dimer of above-mentioned polyisocyanate, Trimer, biuret, allophanate, urea diketone, urea imines, isocyanuric acid ester, oxadiazines triketone, polymethylene polyphenyl base gather Isocyanates (thick MDI, polymeric MDI), thick TDI etc..
As above-mentioned polyisocyanate and its derivative, it can individually use or two or more can also be used simultaneously.Separately Outside, in these polyisocyanate, as above-mentioned polyisocyanate compounds (c1), there is nonionic hydrophilic radical from what is obtained Blocked polyisocyanate compound (C1) be not likely to produce when heated from the aspect of flavescence, preferred aliphat diisocyanate Ester, alicyclic diisocyanate and their derivative.Wherein, from the viewpoint of the flexibility of the film formed improves, Further preferred aliphatic diisocyanate and its derivative.
In addition, as above-mentioned polyisocyanate compounds (c1), can also use make above-mentioned polyisocyanate and its derivative The prepolymer that object is reacted with the compound that can be reacted with the polyisocyanate under conditions of isocyanate group excess.As The compound that can be reacted with the polyisocyanate, for example,：Compound with hydroxyl, amino isoreactivity hydrogen, specifically For, such as polyalcohol, low molecular weight polyester resin, amine, water etc. can be used.
In addition, as above-mentioned polyisocyanate compounds (c1), the polymerism containing isocyanate group can also be used not The polymer of saturation monomer is somebody's turn to do the polymerism unsaturated monomer containing isocyanate group with being somebody's turn to do polymerizeing containing isocyanate group The copolymer of polymerism unsaturated monomer beyond property unsaturated monomer.
From the reactivity of the obtained blocked polyisocyanate compound (C1) with nonionic hydrophilic radical and contain From the viewpoint of having the composition of the blocked polyisocyanate compound and the intermiscibility of other paint ingredients, above-mentioned polyisocyanate The number average molecular weight of ester compounds (c1) preferably in the range of 300~20,000, more preferably 400~8,000 scope It is interior, further preferably in the range of 500~2,000.
In addition, from the obtained blocked polyisocyanate compound (C1) with nonionic hydrophilic radical reactivity with And should have the blocked polyisocyanate compound (C1) of nonionic hydrophilic radical and the sight of the intermiscibility of other paint ingredients It puts and considers, model of the average isocyanate ester functional group number in above-mentioned polyisocyanate compounds (c1) preferably 1 molecule 2~100 In enclosing.As lower limit, from improving the anti-of the obtained blocked polyisocyanate compound (C1) with nonionic hydrophilic radical From the viewpoint of answering property, more preferable 3.As the upper limit, from blocked polyisocyanate of the manufacture with nonionic hydrophilic radical From the viewpoint of gelation being prevented during compound (C1), more preferable 20.
Active hydrogen-contg compound (c2) with nonionic hydrophilic radical
As the active hydrogen-contg compound with nonionic hydrophilic radical, such as preferably containing using polyoxyalkylenes Active dydrogen compounds.As above-mentioned polyoxyalkylenes, for example,：Polyoxyethylene groups, polyoxypropylene base, polyoxyethylene (oxypropylene) base etc., these, which may be used alone or in combination, uses two or more.Wherein, there is nonionic hydrophilic group from what is obtained From the viewpoint of the storage stability of the blocked polyisocyanate compound (C1) of group, preferably have polyoxyethylene groups contains activity Hydrogen compound.
From the storage stability of the obtained blocked polyisocyanate compound (C1) with nonionic hydrophilic radical and The viewpoints such as the water resistance of the film formed consider that the above-mentioned active hydrogen-contg compound with polyoxyethylene groups preferably has 3 Above continuous oxyethylene group preferably has 5~100 continuous oxyethylene groups, more preferably has 8~45 continuously Oxyethylene group.
In addition, the above-mentioned active hydrogen-contg compound with polyoxyethylene groups can also contain in addition to continuous oxyethylene group There is the oxyalkylene group beyond oxyethylene group.As the oxyalkylene group beyond the oxyethylene group, for example,：Oxypropylene group, Oxygen cyclobutenyl, oxygen hexenyl etc..From the moisture of the obtained composition containing blocked polyisocyanate compound dissipate after storage From the viewpoint of stability, the oxyethylene group in oxyalkylene in the above-mentioned active hydrogen-contg compound with polyoxyethylene groups rubs That ratio is preferably in the range of 20~100 moles of %, more preferably in the range of 50~100 moles of %.If oxyalkylene group In oxyethylene group molar ratio less than 20 moles of %, then can not fully assign hydrophily, what is obtained has nonionic parent The storage stability of the blocked polyisocyanate compound (C1) of water base group reduces sometimes.
In addition, the stable storing from the obtained blocked polyisocyanate compound (C1) with nonionic hydrophilic radical Property and the water resistance of film that is formed from the viewpoint of, the above-mentioned active hydrogen-contg compound with nonionic hydrophilic radical Number-average molecular weight is preferably in the range of 200~2,000.As the lower limit of number-average molecular weight, there is nonionic from what is obtained From the viewpoint of the storage stability of the blocked polyisocyanate compound (C1) of hydrophilic radical, more preferably 300, it is further excellent Elect 400 as.As the upper limit, from the viewpoint of the water resistance of the film formed from aqueous 1st pigmented finiss (X) by the present invention, More preferably 1,500, further preferably 1,200.
As the above-mentioned active hydrogen-contg compound with nonionic hydrophilic radical, for example,：Polyethyleneglycol Polyalkylene glycol monoalkyls ether (the alias such as methyl ether and polyethyleneglycol ether：ω-alkoxy polyoxy), polypropylene glycol list first Polypropylene glycols monoalky lether (the alias such as ether and polypropylene glycol list ether：ω-alkoxy polyoxypropylene), ω-methoxyl group polyoxy second ω-the alkoxy polyoxies (oxypropylene) such as alkene (oxypropylene), ω-ethyoxyl polyoxyethylene (oxypropylene), polyethylene glycol (the third two Alcohol) polyethylene glycol (propylene glycol) monoalky lether such as monomethyl ether, the single ether of polyethylene glycol (propylene glycol), polyethylene glycol, polypropylene glycol, Polyethylene glycol (propylene glycol), α-(aminoalkyl)-ω-alkoxy polyoxy, α-(aminoalkyl)-ω-alkoxy polyoxy third Alkene, α-(aminoalkyl)-ω-alkoxy polyoxy (oxypropylene) etc., these, which may be used alone or in combination, uses two or more. Wherein, preferably poly glycol monomethyl ether, polyethyleneglycol ether and polyethylene glycol, more preferable poly glycol monomethyl ether.
In addition, in the present specification, " polyethylene glycol (propylene glycol) " refers to the copolymer of ethylene glycol and propylene glycol, comprising embedding Section any one of copolymer and random copolymer.
In addition, the market sale product as above-mentioned poly glycol monomethyl ether, for example,：Japan Oil Co manufactures " UNIOX M-400 ", " UNIOX M-550 ", " UNIOX M-1000 ", " UNIOX M-2000 " etc..In addition, as above-mentioned poly- The market sale product of ethylene glycol, for example,：" PEG#200 ", " PEG#300 ", " PEG# of Japan Oil Co's manufacture 400 ", " PEG#600 ", " PEG#1000 ", " PEG#1500 ", " PEG#1540 ", " PEG#2000 " etc..
From the storage stability of the obtained blocked polyisocyanate compound (C1) with nonionic hydrophilic radical and Curability and by the adhesion of the film that is formed of aqueous 1st pigmented finiss (X) of the present invention, flatness, distinctiveness and resistance to From the viewpoint of aqueous, a part of isocyanate group in polyisocyanate compounds (c1) are made has nonionic with above-mentioned In the case of active hydrogen-contg compound (c2) reaction of hydrophilic radical, for isocyanate compound (c1) with having nonionic The reaction ratio of the active hydrogen-contg compound (c2) of hydrophilic radical, with 1 mole of isocyanic acid in polyisocyanate compounds (c1) The molal quantity of reactive hydrogen on the basis of ester group in preferred active hydrogen-contg compound is in the range of 0.03 mole~0.6 mole.Make For the upper limit, from the curability of the obtained blocked polyisocyanate compound (C1) with nonionic hydrophilic radical and by this hair From the viewpoint of the water resistance for the film that bright aqueous 1st pigmented finiss (X) is formed, more preferably 0.4, further preferably 0.3.As lower limit, from the stable storing of the obtained blocked polyisocyanate compound (C1) with nonionic hydrophilic radical Property and by the adhesion of the film that is formed of aqueous 1st pigmented finiss (X) of the present invention, flatness, distinctiveness and water resistance Viewpoint considers, is more preferably 0.04, further preferably 0.05.
End-capping reagent (c3)
As end-capping reagent, for example,：Phenol system, alcohol system, active methylene group system, mercaptan system, sour amide system, sour acyl are sub- Amine system, imidazoles system, Urea Series, oxime system, carbamic acid system, amine system, imines system etc., these can be used alone or simultaneously use 2 kinds More than.More specific end-capping reagent is as follows.
(1) phenol system；Phenol, cresols, ethyl -phenol, butylphenol etc.,
(2) alcohol system；Ethylene glycol, benzyl alcohol, methanol, ethyl alcohol etc.,
(3) active methylene group system；Diester malonate, acetoacetic ester, isobutyryl acetic acid esters etc.,
(4) mercaptan system；Butyl mercaptan, lauryl mercaptan etc.,
(5) sour amide system；Antifebrin, amide, epsilon-caprolactams, δ-valerolactam, butyrolactam etc.,
(6) acid imide system；Succinimide, maleimide etc.,
(7) imidazoles system；Imidazoles, 2-methylimidazole etc.,
(8) Urea Series；Urea, thiocarbamide, ethylidene-urea etc.,
(9) oxime system；Formaldoxime, acetaldoxime, methyl ethyl ketone oxime, cyclohexyl ketoxime etc.,
(10) carbamic acid system；N- phenylcarbamic acid phenyl esters etc.,
(11) amine system；Diphenylamine, aniline, carbazole etc.,
(12) imines system；Aziridine, polyethyleneimine etc..
Catalysts are optionally used using the sealing endization reaction of the isocyanate group of end-capping reagent (c3).It is anti-as this Catalyst is answered, for example,：Metal hydroxides, metal alkoxide, metal carboxylate, metal acetyl acetate, salt Hydroxide, carboxylate, the metal salt of activity methene compound, the salt of activity methene compound, amino silicone alkanes, The alkali compounds such as amine, phosphine.Wherein, as salt, preferably ammonium salt, phosphonium salts, sulfonium salt.In general, with polyisocyanate chemical combination On the basis of total solid constituent quality of object (c1) and end-capping reagent (c3), the usage amounts of the catalysts preferably 10ppm~ In the range of 10,000ppm, further preferably in the range of 20ppm~5,000ppm.
In addition, the sealing endization reaction using the isocyanate group of above-mentioned end-capping reagent (c3) can carry out at 0 DEG C~150 DEG C, Solvent can also be used.In this case, as solvent, preferably non-protonic solvent, particularly preferred ester, ether, N- alkyl acyls Amine, ketone etc..If reaction is carried out according to target, can will be used as by adding sour ingredient in the alkali compounds of catalyst With stop reaction.
In using the reaction of the sealing endization of the isocyanate group of end-capping reagent (c3), the usage amount of end-capping reagent (c3) is not special It limits, preferably with respect to 1 mole isocyanate base in polyisocyanate compounds (c1) using 0.1 mole~3 moles, preferably Use 0.2 mole~2 moles.In addition, the end-capping reagent with the isocyanate group reaction in polyisocyanate compounds (c1) can not To be removed after reaction in sealing endization.
Wherein, from the viewpoint of the curability at low temperatures for the film that aqueous 1st pigmented finiss (X) by the present invention is formed, End-capping reagent (c3) is preferably active methylene group system.
From the viewpoint of the stability of aqueous 1st pigmented finiss (X) of the present invention, as with nonionic hydrophilic group The particularly preferred form of the blocked polyisocyanate compound (C1) of group, can enumerate：With shown in the following general formula (IV) Blocked isocyanate base leads to nonionic hydrophilic radical and blocked polyisocyanate compound (C1-1) and with following Blocked isocyanate base shown in formula (V) and the blocked polyisocyanate compound (C1-2) with nonionic hydrophilic radical.
[chemical formula 1]
[in formula (IV), R1It independently represents the alkyl of carbon number 1~12, may be the same or different.]
[chemical formula 2]
[in formula (V), R6And R7Independently represent the alkyl of carbon number 1~12.]
Blocked polyisocyanate compound (C1-1) with nonionic hydrophilic radical
Blocked polyisocyanate compound (C1-1) with nonionic hydrophilic radical is with above-mentioned logical formula (IV) institute The blocked polyisocyanate compound of the blocked isocyanate base shown.
Wherein, the above-mentioned end-capping reagent (c3) of one of raw material as the blocked polyisocyanate compound, from usable energy From the aspect of the sealing end immunomodulator compounds of enough active methylene group classes relatively easily manufactured, R1The preferably alkane of carbon number 1~3 Base.Wherein, from improving obtained blocked polyisocyanate compound (C1) with nonionic hydrophilic radical and other coating From the viewpoint of the intermiscibility of ingredient, R1The preferably alkyl of carbon number 2 or 3 has nonionic hydrophilic group from what is obtained Group blocked polyisocyanate compound (C1) storage stability and by the present invention aqueous 1st pigmented finiss (X) formed Film flatness and distinctiveness from the viewpoint of, R1Further preferably isopropyl.
The above-mentioned blocked polyisocyanate compound (C1-1) with nonionic hydrophilic radical for example can be above-mentioned by making Polyisocyanate compounds (c1) and active hydrogen-contg compound (c2) with nonionic hydrophilic radical with as end-capping reagent (c3) the dialkyl malonate reaction of the alkyl with carbon number 1~12 obtains.
As above-mentioned dialkyl malonate, for example,：Dimethyl malenate, diethyl malonate, malonic acid Di-n-propyl ester, Diisopropyl malonate, malonic acid di-n-butyl, malonic acid diisobutyl ester, malonic acid di-secondary butyl ester, malonic acid two The tert-butyl ester, two n-pentyl ester of malonic acid, the just own ester of malonic acid two, malonic acid two (2- ethylhexyls) ester etc., these can individually make With or two or more is applied in combination.Wherein, preferably dimethyl malenate, diethyl malonate, malonic acid di-n-propyl ester, malonic acid Diisopropyl ester, malonic acid di-n-butyl, malonic acid diisobutyl ester, malonic acid di-secondary butyl ester, malonic acid di tert butyl carbonate, more preferable third Diethyl adipate, malonic acid di-n-propyl ester, Diisopropyl malonate, further preferred Diisopropyl malonate.
Blocked polyisocyanate compound (C1-2) with nonionic hydrophilic radical
Blocked polyisocyanate compound (C1-2) with nonionic hydrophilic radical is with shown in above-mentioned logical formula (V) Blocked isocyanate base blocked polyisocyanate compound.
Wherein, the above-mentioned end-capping reagent (c3) of one of raw material as the blocked polyisocyanate compound, from usable energy From the aspect of the sealing end immunomodulator compounds of enough active methylene group classes relatively easily manufactured, R6And R7Preferably carbon number 1~3 Alkyl.Wherein, from improve obtained blocked polyisocyanate compound (C1) with nonionic hydrophilic radical with it is other From the viewpoint of the intermiscibility of paint ingredient, R6 and R7 are preferably the alkyl of carbon number 2 or 3, have nonionic from what is obtained Property hydrophilic radical blocked polyisocyanate compound (C1) storage stability, by the present invention aqueous 1st pigmented finiss (X) From the viewpoint of the flatness and distinctiveness of the film of formation, R6And R7Further preferably isopropyl.
The above-mentioned blocked polyisocyanate compound (C1-2) with nonionic hydrophilic radical for example can be above-mentioned by making Polyisocyanate compounds (c1) and active hydrogen-contg compound (c2) with nonionic hydrophilic radical with as end-capping reagent (c3), the isobutyryl of the acetoacetic ester of alkyl with carbon number 1~12 or the alkyl with carbon number 1~12 Acetic acid esters reaction obtains.Wherein, as end-capping reagent (c3), it is preferable to use the isobutyryls of the alkyl with carbon number 1~12 Yl acetate is reacted to obtain.
As above-mentioned isobutyryl acetic acid esters, for example,：Isobutyryl methyl acetate, isobutyryl acetic acid second Ester, isobutyryl n-propyl acetate, isobutyryl isopropyl acetate, isobutyryl n-butyl acetate, isobutyryl Sucrose Acetate Ester, isobutyryl sec-butyl acetate, isobutyryl tert-butyl acetate, isobutyryl n-amyl acetate, isobutyryl acetic acid just oneself Ester, isobutyryl acetic acid 2- ethylhexyls, isobutyryl phenylacetate, isobutyryl benzyl acetate etc., these can be used alone Or two or more is applied in combination.Wherein, preferably isobutyryl methyl acetate, ethyl isobutyryl acetate and isobutyryl acetic acid are different Propyl ester.
As above-mentioned acetoacetic ester, for example,：Methyl acetoacetate, ethyl acetoacetate, acetoacetate are just Propyl ester, isopropyl acetoacetate, acetoacetate N-butyl, isobutyl acetoacetate, the secondary butyl ester of acetoacetate, the tertiary fourth of acetoacetate The just own ester of ester, acetoacetate n-pentyl ester, acetoacetate, acetoacetate 2- ethylhexyls, acetoacetate phenyl ester, acetoacetate benzene first Ester etc., these can be used alone or two or more is applied in combination.Wherein, preferably methyl acetoacetate, ethyl acetoacetate and Isopropyl acetoacetate.
In the present invention, particularly from the aspect of stability in water, as with nonionic hydrophilic radical Blocked polyisocyanate compound (C), it is preferable to use further by secondary alcohol (c4) with it is above-mentioned have nonionic hydrophilic radical Blocked polyisocyanate compound (C1) react the obtained blocked polyisocyanate with nonionic hydrophilic radical Close object (following, the blocked polyisocyanate compound with nonionic hydrophilic radical as above obtained is known as " (C2) ").
Blocked polyisocyanate compound (C2) with nonionic hydrophilic radical
Blocked polyisocyanate compound (C2) with nonionic hydrophilic radical for example can be above-mentioned with non-by making The blocked polyisocyanate compound (C1) of ionic hydrophilic radical is come with secondary alcohol (c4) reaction shown in the following general formula (VI) It arrives.
[chemical formula 3]
[in formula (VI), R2、R4And R5Independently represent the alkyl of carbon number 1~12, R3Represent carbon number 1~12 The alkylidene of straight-chain or branched.]
Secondary alcohol (c4)
Secondary alcohol (c4) is above-mentioned logical formula (VI) compound represented.Wherein, it is above-mentioned with nonionic hydrophilic group from improving From the viewpoint of the blocked polyisocyanate compound (C1) of group and the reactivity of above-mentioned secondary alcohol (c4), R2Preferably methyl.Separately Outside, if R3、R4And R5Respective carbon number is more, then the blocked polyisocyanate with nonionic hydrophilic radical obtained The polarity of compound (C2) reduces, and is reduced sometimes with the intermiscibility of other paint ingredients, therefore, R3Preferably carbon number 1~3 Alkylidene, R4And R5Preferably methyl.
As above-mentioned secondary alcohol (c4), for example,：4- methyl -2- amylalcohols, 5- methyl -2- hexanols, 6- methyl -2- heptan Alcohol, 7- methyl-sec-n-octyl alcohol etc., these, which may be used alone or in combination, uses two or more.Wherein, there is nonionic parent above-mentioned After the blocked polyisocyanate compound (C1) of water base group and the reaction of above-mentioned secondary alcohol (c4), by unreacted secondary alcohol (c4) Part or all when being distilled off, from being easier to from the aspect of removing the secondary alcohol (c4), more preferably have more low-boiling 4- methyl -2- amylalcohols.
For the blocked polyisocyanate compound (C2) with nonionic hydrophilic radical, from aqueous the of the present invention From the viewpoint of the stability of 1 pigmented finiss (X), as particularly preferred form, can enumerate following compounds (C2-1) and (C2-2)。
Blocked polyisocyanate compound (C2-1) with nonionic hydrophilic radical
Blocked polyisocyanate compound (C2-1) with nonionic hydrophilic radical specifically for example can be by making Described in the explanation of the above-mentioned blocked polyisocyanate compound (C1) with nonionic hydrophilic radical with the following general formula (IV) blocked isocyanate base shown in and the blocked polyisocyanate compound (C1-1) with non-ionic hydrophilic group and upper Secondary alcohol (c4) reaction is stated to obtain.
[chemical formula 4]
[in formula (IV), R1It independently represents the alkyl of carbon number 1~12, may be the same or different.]
At this point, the sealing end isocyanide in the above-mentioned blocked polyisocyanate compound (C1-1) with nonionic hydrophilic radical R in perester radical1At least one party be substituted by group shown in the following general formula (VII).
[chemical formula 5]
[in formula (VII), R2、R4And R5Independently represent the alkyl of carbon number 1~12, R3Represent carbon number 1~12 Straight-chain or branched alkylidene.]
In addition, in this case, obtained blocked polyisocyanate compound has the sealing end shown in the following general formula (I) Blocked isocyanate base shown in isocyanate group or the following general formula (II).
[chemical formula 6]
[in formula (I), R1、R2、R4And R5Independently represent the alkyl of carbon number 1~12, R3Expression carbon number 1~ 12 straight-chain or the alkylidene of branched.]
[chemical formula 7]
[in formula (II), R2、R3、R4And R5With above-mentioned R2、R3、R4And R5It is identical.]
The above-mentioned blocked polyisocyanate compound (C1-1) with nonionic hydrophilic radical and the reaction of secondary alcohol (c4) There is no particular limitation, as long as for example can be by the blocked polyisocyanate compound (C1-1) with nonionic hydrophilic radical In blocked isocyanate base in R1At least one method for being substituted by the group shown in above-mentioned logical formula (VII).Its In, preferably by the way that heat and depressurize etc. will be from the blocked polyisocyanate compound (C1-1) with nonionic hydrophilic radical In R1, at least one some or all of alcohol be distilled off to the external promotion reaction of system, obtain having above-mentioned Logical formula (I) or the blocked isocyanate base shown in (II) and the side of the blocked polyisocyanate compound of nonionic hydrophilic radical Method.
As above-mentioned manufacturing method, specifically, 20~150 DEG C, preferably optionally subtract at a temperature of 75~95 DEG C Pressure, with 5 minutes~20 when small, preferably 10 minutes~10 it is small when by some or all removings of above-mentioned alcohol.If above-mentioned temperature Spend low, the then exchange reaction of the alkoxy in the blocked polyisocyanate compound (C1-1) with nonionic hydrophilic radical Slack-off, manufacture efficiency reduces, on the other hand, if above-mentioned temperature is excessively high, the obtained envelope with nonionic hydrophilic radical The decomposition deterioration for holding polyisocyanate compounds (C2) is violent, and curability reduces sometimes, this is not desired.
Blocked polyisocyanate compound (C2-2) with nonionic hydrophilic radical
In addition, the blocked polyisocyanate compound (C2-2) with nonionic hydrophilic radical specifically can for example lead to Cross make described in the explanation of the above-mentioned blocked polyisocyanate compound (C1) with nonionic hydrophilic radical with following Blocked isocyanate base shown in logical formula (V) and the blocked polyisocyanate compound (C1-2) with non-ionic hydrophilic group and Above-mentioned secondary alcohol (c4) reaction obtains.
[chemical formula 8]
[in formula (V), R6And R7Independently represent the alkyl of carbon number 1~12.]
In this case, the sealing end isocyanide in the above-mentioned blocked polyisocyanate compound (C1-2) with hydrophilic radical R in perester radical7The group being substituted by shown in the following general formula (VII).
[chemical formula 9]
[in formula (VII), R2、R4And R5Independently represent the alkyl of carbon number 1~12, R3Represent carbon number 1~12 Straight-chain or branched alkylidene.]
In this case, the blocked polyisocyanate compound (C1-2) obtained has shown in the following general formula (III) Blocked isocyanate base.
[chemical formula 10]
[in formula (III), R2、R3、R4And R5With above-mentioned R2、R3、R4And R5It is identical, R6Represent carbon number 1~12 Alkyl.]
The reaction of above-mentioned blocked polyisocyanate compound (C1-2) and secondary alcohol (c4) with nonionic hydrophilic radical It is not particularly limited, as long as it for example can will be in the blocked polyisocyanate compound (C1-2) with nonionic hydrophilic radical Blocked isocyanate base in R7It is substituted by the method for the group shown in above-mentioned logical formula (VII).Wherein, preferably by adding Heat and decompression etc. will be from the R in the blocked polyisocyanate compound (C1-2) with hydrophilic radical7, the part of alcohol or Person be all distilled off, to system external promotion reaction, obtaining having the blocked isocyanate base shown in above-mentioned logical formula (III) and The method of blocked polyisocyanate compound (C2-2) with nonionic hydrophilic radical.
As above-mentioned manufacturing method, specifically, be suitble to 20~150 DEG C, preferably at a temperature of 75~95 DEG C optionally Ground depressurizes, by 5 minutes~20 when small, preferably through 10 minutes~10 when small by some or all removings of above-mentioned alcohol. If above-mentioned temperature is too low, the alkoxy in the blocked polyisocyanate compound (C1-2) with nonionic hydrophilic radical Exchange reaction become slow, manufacture efficiency reduce, on the other hand, if above-mentioned temperature is excessively high, obtain have nonionic Property hydrophilic radical blocked polyisocyanate compound (C2) decomposition deterioration it is violent, curability reduces sometimes, this is not institute's phase It hopes.
In addition, from the reactivity of the obtained blocked polyisocyanate compound (C) with nonionic hydrophilic radical and From the viewpoint of manufacture efficiency, in the manufacture of the blocked polyisocyanate compound (C2) with nonionic hydrophilic radical , the mixing ratio of the above-mentioned blocked polyisocyanate compound (C1) with nonionic hydrophilic radical and secondary alcohol (c4), with On the basis of 100 mass parts of solid constituent of blocked polyisocyanate compound (C1) with nonionic hydrophilic radical, secondary alcohol (c4) preferably in the range of the mass parts of 5 mass parts~500, further preferably in the range of the mass parts of 10 mass parts~200. When less than 5 mass parts, there is the blocked polyisocyanate compound (C1) of hydrophilic radical and the reaction speed of secondary alcohol (c4) to have When it is excessively slow.In addition, if more than 500 mass parts, then the sealing end polyisocyanate with nonionic hydrophilic radical generated The concentration of ester compounds (C2) becomes too low, and manufacture efficiency reduces sometimes.
In addition, in the above-mentioned blocked polyisocyanate compound (C1) with nonionic hydrophilic radical and secondary alcohol (c4) In reaction, in order to adjust the molecular weight of the blocked polyisocyanate compound (C2) with nonionic hydrophilic radical, Ke Yi Polyol is added in the blocked polyisocyanate compound (C1) and secondary alcohol (c4) with nonionic hydrophilic radical Above-mentioned removing operation is carried out after object.
Compound (C2-1) or compound in blocked polyisocyanate compound (C) with nonionic hydrophilic radical (C2-2) in water stability is especially excellent, thus it is speculated that the reasons why being such：Due to nonionic hydrophilic radical, More steadily exist in water, and then, due to comprising the alkyl with branched structure, the polarity of blocked isocyanate base is low, Not facile hydrolysis.
In one embodiment, the blocked polyisocyanate compound (C) with nonionic hydrophilic radical is with choosing From the blocked isocyanate base shown in the following general formula (I), the blocked isocyanate base shown in the following general formula (II) and following logical The blocked polyisocyanate compound of at least one of blocked isocyanate base shown in formula (III) blocked isocyanate base.
[chemical formula 11]
[in formula (I), R1、R2、R4And R5Independently represent the alkyl of carbon number 1~12, R3Expression carbon number 1~ 12 straight-chain or the alkylidene of branched.]
[chemical formula 12]
[in formula (II), R2、R3、R4And R5With above-mentioned R2、R3、R4And R5It is identical.]
[chemical formula 13]
[in formula (III), R2、R3、R4And R5With above-mentioned R2、R3、R4And R5It is identical, R6Represent carbon number 1~12 Alkyl.]
From with other paint ingredients intermiscibility, by the present invention the coating that is formed of aqueous 1st pigmented finiss (X) it is smooth Property, the viewpoints such as distinctiveness, adhesion, water resistance and chipping resistance consider, have nonionic hydrophilic radical sealing end gather it is different The number-average molecular weight of cyanate esters (C) is preferably in the range of 600~30,000.From the intermiscibility with other paint ingredients And from the viewpoint of the flatness and distinctiveness of film formed by aqueous 1st pigmented finiss (X) of the present invention, as above-mentioned The upper limit of number-average molecular weight is more preferably 10,000, and further preferably 5,000.In addition, it is coloured from by the aqueous 1st of the present invention the From the viewpoint of the adhesion of film, water resistance and chipping resistance that coating (X) is formed, lower limit is more preferably 900, further excellent Elect 1,000 as.
In addition, the above-mentioned blocked polyisocyanate compound (C) with nonionic hydrophilic radical can also in advance and table Face activating agent mixing.In this case, from the viewpoint of the stability of aqueous 1st pigmented finiss (X) of the present invention, the table Face activating agent is preferably nonionic surfactant.
The present invention aqueous 1st pigmented finiss (X) in, from the chipping resistance of obtained film, adhesion, retouching property, From the aspect of weatherability and ethanol petrol resistant, using the resin solid content quality total amount in the 1st pigmented finiss (X) as base Standard, the content of the above-mentioned blocked polyisocyanate compound (C) with nonionic hydrophilic radical are suitably for the matter of 5 mass %~40 % is measured, is preferably the mass % of 7 mass %~35, the mass % of further preferably 10 mass %~30.
Conductive pigment (D)
It is not particularly limited as conductive pigment (D), as long as electric conductivity, particle can be assigned to the film formed Shape, sheet, the pigment of any shape in fiber (include whisker) shape can be used.Specifically, for example,：It is conductive The conductive carbons such as property carbon black, carbon nanotubes, carbon nano-fiber, carbon micro-coil；The metal powders such as silver, nickel, copper, graphite, aluminium, and then, It can enumerate：Antimony-doped tin oxide, phosphorus doping tin oxide carried out acicular titanium oxide, the oxidation that surface is coated with tin oxide/antimony Antimony, zinc antimonates, tin indium oxide, the pigment in the whisker surface of carbon or graphite coating tin oxide etc.；In the mica surface quilt of sheet Cover the pigment of the conductive metal oxides such as tin oxide or antimony-doped tin oxide；Contain on TiO 2 particles surface tin oxide and Phosphorus, conductive pigment etc..These can individually using or two or more is applied in combination.It wherein, can be particularly preferred Use conductive carbon.
From the aspect of the electric conductivity of obtained film and light transmittance, consolidated with the resin in aqueous 1st pigmented finiss (X) On the basis of body composition quality total amount, the above-mentioned conductive pigment in aqueous 1st pigmented finiss (X) used in the present invention contains Amount is suitably for the mass % of 0.5 mass %~40, is preferably the mass % of 1 mass %~35, the matter of further preferably 3 mass %~30 Measure %.
In one embodiment, on the basis of the resin solid content quality total amount in aqueous 1st pigmented finiss (X), this Aqueous 1st pigmented finiss (X) used in invention containing 10 mass %~60 mass % chlorine-free polyolefin-based resins (A), The mass %'s of the waterborne polyurethane resin (B) of the mass % of 10 mass %~50,5 mass %~40 has nonionic hydrophilic radical Blocked isocyanate compounds (C) and the mass % of 0.5 mass %~40 conductive pigment (D).
Other ingredients
Aqueous 1st pigmented finiss (X) used in the present invention is with above-mentioned chlorine-free polyolefin-based resins (A), specific Waterborne polyurethane resin (B), the blocked polyisocyanate compound (C) with non-aqueous hydrophilic radical, conductive pigment (D) are Required ingredient, can further contain the sealing end beyond hydroxy acryl acid resin, hydroxyl group containing polyester resin, ingredient (C) and gather The resin components such as isocyanate compound, melmac, phenolic resin, polycarbonate resin and epoxy resin.
Hydroxy acryl acid resin can use the water solubility known per se or moisture used in previous water paint Dissipate the hydroxy acryl acid resin of property.Hydroxy acryl acid resin for example can be by making hydroxyl polymerism unsaturated monomer and can The method, such as both known by its own with other polymerism unsaturated monomers of hydroxyl polymerism unsaturated monomer copolymerization The methods of polymerisation in solution, is copolymerized to manufacture.
Hydroxyl polymerism unsaturated monomer is unsaturated to be respectively provided with 1 or more hydroxyl and polymerism in 1 molecule The compound of key, for example,：(methyl) Hydroxyethyl Acrylate, (methyl) hydroxypropyl acrylate, (methyl) propylene The monoesters compound of the glycol such as sour hydroxybutyl and polyethyleneglycol (methyl) acrylate and acrylic or methacrylic acid；Make Compound that 6-caprolactone is formed with the progress ring-opening polymerisation of the monoesters compound of above-mentioned polyalcohol and acrylic or methacrylic acid etc..
The other polymerism unsaturated monomers that can be copolymerized with hydroxyl polymerism unsaturated monomer can be according to hydroxyl propylene The desired characteristic of acid resin is suitably selected and used.The specific embodiment of the monomer is set forth below.These can individually make With or two or more is applied in combination.
(i) (methyl) acrylic acid alkyl or cycloalkyl ester：Such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) the just own ester of acrylic acid, (methyl) n-octyl, (methyl) acrylic acid 2- ethyl hexyls Ester, (methyl) acrylic acid nonyl ester, (methyl) dodecylacrylate, (methyl) tridecyl acrylate, (methyl) propylene Sour stearyl, (methyl) acrylic acid iso stearyl ester, (methyl) cyclohexyl acrylate, (methyl) acrylic methyl cyclohexyl, (methyl) t-butylcyclohexyl ester, (methyl) acrylic acid cyclododecane base ester, (methyl) acrylic acid tricyclodecyl etc..
(ii) there is the polymerism unsaturated monomer of isobornyl：Such as (methyl) isobornyl acrylate etc..
(iii) there is the polymerism unsaturated monomer of adamantyl：Such as (methyl) acrylic acid adamantane esters etc..
(iv) there is the polymerism unsaturated monomer of tricyclic decenyl：Such as (methyl) acrylic acid tricyclodecenyl esters etc..
(v) the polymerism unsaturated monomer containing aromatic rings：Such as (methyl) benzyl acrylate, styrene, Alpha-Methyl benzene second Alkene, vinyltoluene etc..
(vi) there is the polymerism unsaturated monomer of alkoxysilyl：Such as vinyltrimethoxysilane, ethylene Ethyl triethoxy silicane alkane, vinyl three (2- methoxy ethoxies) silane, γ-(methyl) acryloxypropyl trimethoxy silicon Alkane, γ-(methyl) acryloxypropyl triethoxysilane etc..
(vii) there is the polymerism unsaturated monomer of fluoro-alkyl：Such as (methyl) perfluoroethyl butyl ethyl ester, (first Base) (methyl) perfluoroalkyl acrylate such as perfluoroethyl octyl group ethyl ester；Fluoroolefin etc..
(viii) there is the polymerism unsaturated monomer of the optical polymerisms functional groups such as Maleimido.
(ix) vinyl compound：Such as n-vinyl pyrrolidone, ethylene, butadiene, chlorobutadiene, vinyl propionate Ester, vinyl acetate etc..
(x) the polymerism unsaturated monomer of phosphorous acidic group：Such as 2- acryloyl-oxyethyls phosphate ester acid, 2- methyl-props Alkene trimethylammonium phosphate ester acid, 2- acryloxypropyls phosphate ester acid, 2- methacryloxypropyl acid phosphorus It is sour cruel etc..
(xi) carboxylic polymerism unsaturated monomer：Such as (methyl) acrylic acid, maleic acid, crotonic acid, propenoic acid beta- Carboxyethyl etc..
(xii) nitrogenous polymerism unsaturated monomer：Such as (methyl) acrylonitrile, (methyl) acrylamide, (methyl) propylene Sour N, N- dimethylamino ethyl ester, (methyl) acrylic acid N, N- diethylamino ethyl ester, N, N- dimethylaminopropyls (methyl) Acrylamide, di-2-ethylhexylphosphine oxide (methyl) acrylamide, ethylenebis (methyl) acrylamide, 2- (methacryloxy) ethyl Addition product of trimethyl ammonium chloride, (methyl) glycidyl acrylate and amine etc..
(xiii) there is the polymerism unsaturated monomer of at least two polymerism unsaturated group in 1 molecule：For example, (first Base) allyl acrylate, 1,6-HD two (methyl) acrylate etc..
(xiv) the polymerism unsaturated monomer containing epoxy group：Such as (methyl) glycidyl acrylate, (methyl) propylene Sour Beta-methyl ethylene oxidic ester, (methyl) acrylic acid 3,4- epoxycyclohexanecarboxylates, (methyl) acrylic acid 3,4- epoxycyclohexyls Ethyl ester, (methyl) acrylic acid 3,4- epoxycyclohexyls propyl ester, allyl glycidyl ether etc..
(xv) there is (methyl) acrylate of molecular end for the polyoxyethylene chain of alkoxy.
(xvi) there is sulfonic polymerism unsaturated monomer：Such as 2- acrylamido -2- methyl propane sulfonic acids, (first Base) acrylic acid 2- sulphurs ethyl ester, allyl sulphonic acid, 4- styrene sulfonic acids etc.；Sodium salt and ammonium salt of these sulfonic acid etc..
(xvii) there is the polymerism unsaturated monomer of ultraviolet-absorbing functional group：Such as 2- hydroxyls -4- (3- methyl-props Alkene acyloxy -2- hydroxy propyloxy groups) benzophenone, 2- hydroxyls -4- (3- acryloxy -2- hydroxy propyloxy groups) benzophenone, 2,2 '-dihydroxy -4- (3- methacryloxy -2- hydroxy propyloxy groups) benzophenone, 2,2 '-dihydroxy -4- (3- acryloyls Oxygroup -2- hydroxy propyloxy groups) benzophenone, 2- (2 '-hydroxyl -5 '-methaciylyloxyethylphenyl) -2H- benzotriazole Deng.
(xviii) photostability polymerism unsaturated monomer：Such as five first of 4- (methyl) acryloxies -1,2,2,6,6- Phenylpiperidines, 4- (methyl) acryloxy -2,2,6,6- tetramethyl piperidines, 4- cyano -4- (methyl) Acryloyl amino -2,2, 6,6- tetramethyl piperidines, 1- (methyl) acryloyl group -4- (methyl) Acryloyl amino -2,2,6,6- tetramethyl piperidines, 1- (first Base) acryloyl group -4- cyano -4- (methyl) Acryloyl amino -2,2,6,6- tetramethyl piperidines, 4- crotons acyloxy -2,2, 6,6- tetramethyl piperidines, 4- crotonocyl amino -2,2,6,6- tetramethyl piperidines, 1- crotonocyl -4- crotons acyloxy -2,2,6,6- Tetramethyl piperidine etc..
(xix) there is the polymerism unsaturated monomer of carbonyl：Such as methacrylaldehyde, Diacetone Acrylamide, diacetone methyl Acrylamide, acetoacetoxyethyl methacrylate, formoxyl styrene, the vinyl alkane with 4~7 carbon atoms Base ketone (for example, ethenyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone) etc..
(xx) there is the polymerism unsaturated monomer of anhydride group：Such as maleic anhydride etc., itaconic anhydride, citraconic anhydride etc..
For hydroxy acryl acid resin, generally be suitable for hydroxyl value in the range of 10~150, be particularly suitable for 50~100 In the range of, acid value is suitble to below 60, is particularly suitable for below 50, weight average molecular weight is suitble to scope 1000~100000 It is interior, be particularly suitable in the range of 2000~60000.
In addition, in the present specification, the weight average molecular weight of above-mentioned hydroxy acryl acid resin and aftermentioned hydroxyl gather When the number-average molecular weight of ester resin and aftermentioned melmac is will use the holding that gel permeation chromatography (GPC) measures Between (holding capacity) according to known to the molecular weight measured in identical conditions standard polystyren retention time (holding capacity) The value for being scaled the molecular weight of polystyrene and acquiring.Specifically, " HLC-8120GPC " (trade name, Tosoh company system is used Make) as gel permeation chromatography device, use " TSKgel G4000HXL ", " TSKgel G3000HXL ", " TSKgel G2500HXL " and " TSKgel G2000HXL " (trade name is the manufacture of Tosoh company) amount to 4 as chromatographic column, use Differential refraction rate is counted as detector, can be in mobile phase：Tetrahydrofuran, measurement temperature：40 DEG C, flow velocity：Under conditions of 1mL/min Measurement.
In aqueous 1st pigmented finiss (X) used in the present invention, from the chipping resistance of obtained film, adhesion, From the aspect of retouching property, weatherability and ethanol petrol resistant, with total resin solid content amount in the 1st pigmented finiss (X) On the basis of, usage amount during using hydroxy acryl acid resin is suitably for the mass % of 5 mass %~35, be preferably 10 mass %~ 25 mass %.
Hydroxyl group containing polyester resin can be dissipated using the water solubility known per se used in current water paint or moisture The hydroxyl group containing polyester resin of property, for example, can by make polyacid and polyalcohol by method known per se hydroxyl excess feelings Esterification is carried out under condition and is obtained.Polyacid is the compound for having in 1 molecule 2 or more carboxyls, for example,：It is adjacent Phthalic acid, M-phthalic acid, terephthalic acid (TPA), tetrahydrophthalic acid, hexahydrophthalic acid, 1,4- hexamethylene dicarboxyls Acid, Pyromellitic Acid, itaconic acid, adipic acid, decanedioic acid, azelaic acid, dodecanedioic acid, dimeric dibasic acid, humic acid, succinic acid, chlorine Bridge acid and their acid anhydride etc..Polyalcohol is the compound for having in 1 molecule 2 or more hydroxyls, for example,：Second Glycol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, butanediol, hexylene glycol, 2- ethyl -2- butyl -1,3- the third two Alcohol, cyclohexanedimethanol, trimethylolethane, trimethylolpropane, pentaerythrite, dipentaerythritol, D-sorbite etc..Such as The introducing of hydroxyl can be carried out by being simultaneously used in the polyalcohol with 3 or more hydroxyls in 1 molecule.In addition, as polyester Resin can also be used and carried out by aliphatic acid such as soya fatty acid, Castor Oil Fatty Acid, dehydrated castor oil fatty acid etc. Modified fatty acid modified polyester resin.In addition, polyester resin can also use butyl glycidyl base ether, alkyl phenyl shrink sweet The epoxides such as oleyl ether, glycidyl neodecanoate are modified.
For hydroxyl group containing polyester resin, usual hydroxyl value is suitble in the range of 10mgKOH/g~160mgKOH/g, is especially suitable Close in the range of 50mgKOH/g~85mgKOH/g, acid value be suitble to below 50mgKOH/g, be particularly suitable for 1mgKOH/g~ In the range of 30mgKOH/g, number-average molecular weight be suitble in the range of 1,000~20,000, be particularly suitable for 1,300~10, In the range of 000.
In aqueous 1st pigmented finiss (X) used in the present invention, from the chipping resistance of obtained film, adhesion, From the aspect of retouching property, weatherability and ethanol petrol resistant, with total resin solid content amount in the 1st pigmented finiss (X) On the basis of, usage amount during using hydroxyl group containing polyester resin is suitably for the mass % of 2 mass %~20, is preferably 5 mass %~15 Quality %.
Sealing endization polyisocyanate compounds beyond ingredient (C) are that the isocyanate group of polyisocyanate compounds is added Obtained from adding end-capping reagent, moreover, the blocked polyisocyanate compound generated by adding is stablized at normal temperatures, but preferably When being heated to sintering temperature (normally about 80 DEG C~about 200 DEG C) of film, end-capping reagent can be dissociated and generated again free different Cyanic acid ester group.As the end-capping reagent of necessary condition as satisfaction, for example,：Phenols, lactams, alcohols, ethers, The end-capping reagents such as oximes, active methylene group class, thio-alcohol, sour amides, acid imide class, amine, imidazoles, pyrazoles.
As melmac, particularly preferably with methyl, ethyl, normal-butyl, isobutyl group, hexyl, 2- ethylhexyls etc. Alkyl carried out the alkyl etherified melamine resin of etherificate.These melmacs can further have methylol, imido Base etc..Melmac generally preferably have number-average molecular weight in the range of 500~5,000, it is particularly preferred with Number-average molecular weight in the range of 800~3,000.
Aqueous 1st pigmented finiss (X) used in the present invention can further contain coloring pigment, extender pigment, organic Additive for coatings such as solvent, silane coupling agent, curing catalysts, tackifier, antifoaming agent, surface conditioner, coalescents etc..
As coloring pigment, for example,：Titanium oxide, carbon black, chrome yellow, loess, yellow iron oxide, hansa yellow, face Expect Huang, chrome orange, molybdate red, forever solid orange, umber, permanent bordeaux, bright famille rose, Fast violet, Methyl Violet Lake, ultramarine, it is Prussian blue, Cobalt blue, phthalocyanine blue, naphthol green, naphthol green, aluminium cream.These can individually using or two or more is applied in combination.
From the viewpoint of the light transmittance of obtained film and retouching property, aqueous 1st coloring used in the present invention When coating (X) contains above-mentioned coloring pigment, on the basis of the resin solid content quality total amount in aqueous 1st pigmented finiss (X), The content of the coloring pigment is suitble in the range of the mass % of 1 mass %~180, preferably the model in the mass % of 2 mass %~140 In enclosing, further preferably in the range of the mass % of 4 mass %~130.
As extender pigment, for example,：Talcum, silica, calcium carbonate, barium sulfate, zinc white (zinc oxide) etc.. These can individually using or two or more is applied in combination.
From the viewpoint of the light transmittance and chipping resistance of obtained film, the used in the present invention the aqueous 1st It is total with the resin solid content quality in aqueous 1st pigmented finiss (X) in the case that color coating (X) contains above-mentioned extender pigment On the basis of amount, the content of the extender pigment is the mass % of 1 mass %~150, is preferably the mass % of 5 mass %~130, further It is preferred that in the range of the mass % of 10 mass %~110.
It is not particularly limited as organic solvent, as long as such as above-mentioned resin component can be mixed and dissolved or scattered Organic solvent, it can be cited for example that Aliphatic hydrocarbon solvents, aromatic hydrocarbon solvent, alcohols solvent, esters solvent, ketone Solvent equal solvent.
As silane coupling agent, for example,：2- (3,4 epoxycyclohexyl) ethyltrialkoxysilanes, 3- epoxies Propoxypropyl trialkoxy silane, 3- glycidoxypropyls dialkoxy silicane, N-2- (amino-ethyl) -3- amino Hydroxypropyl methyl dialkoxy silicane, N-2- (amino-ethyl) -3- aminopropyltrialkoxy silanes, 3- aminopropyl tri-alkoxies Silane, 3- amino propyl methyls dialkoxy silicane, 3- mercaptopropyi methyl dioxanes oxysilane, 3- mercaptopropyi tri-alkoxies Silane, N- phenyl -3- aminopropyltrialkoxy silanes, 3- ureidopropyltrialkoxysilanes, 3- chloropropyl tri-alkoxy silicon Alkane, double (trialkoxysilyl propyl) tetrasulfides, 3- isocyanates propyl trialkoxy silanes etc..These can distinguish It is used singly or in combination two or more.
The solid component concentration of aqueous 1st pigmented finiss (X) is preferably generally the mass % of 20 mass %~70, more preferably The mass % of the mass % of 30 mass %~60, further preferably 35 mass %~60.
The application of aqueous 1st pigmented finiss (X) used in the present invention is not particularly limited, such as can be sprayed by air It applies the coating process such as application, airless spraying application, rotary-atomizing application, curtain painting application and forms wet coating.In these application sides In method, it can also optionally apply electrostatic.Wherein, particularly preferred aerial spraying application.The application of aqueous 1st pigmented finiss (X) It is usually 1 μm~20 μm, the amount specifically for 3 μm~15 μm that amount, which is preferably set to the film thickness based on cured coating film,.Application in this way Aqueous 1st pigmented finiss (X) can form the 1st coloring film.
From the viewpoint of the chipping resistance of the film formed, adhesion, retouching property and weatherability, application aqueous the 1 pigmented finiss (X) and make its cure obtained from cured coating film thickness be 5 μm when being averaged at wavelength 360nm~420nm Light transmittance is suitble to, less than 1%, be particularly suitable for less than 0.5%.Average transmittance can be by adjusting the thickness of cured coating film and being averaged Contained amount of pigment etc. is set in light transmittance.
Here, above-mentioned thickness be the average transmittance of 5 μm of cured coating film at wavelength 360nm~420nm can by with Under method measurement.
First, aqueous 1st pigmented finiss of application in a manner that the coating thickness on polyfluortetraethylene plate when curing is 5 μm (X) and its curing is made.Then, film obtained from curing is removed and recycled, using spectrophotometer measurement wavelength 360nm~ The average transmittance of the scope of 420nm.As above-mentioned spectrophotometer, such as usable " SolidSpec-3700 " (trade name, Shimadzu Seisakusho Ltd. manufactures) etc..
Process (2)
Aqueous 2nd pigmented finiss (Y) of application on the above-mentioned 1st coloring film.
The solid constituent containing ratio of above-mentioned 1st coloring film can be by carrying out before aqueous 2nd pigmented finiss (Y) of application Such as (preheating), air blast etc. are preheated to adjust, but in the present invention, even if after aqueous 1st pigmented finiss (X) of application not It is preheated, also can obtain chipping resistance, adhesion, retouching property, weatherability and the excellent multilayer of ethanol petrol resistant and apply Film.When without preheating, after aqueous 1st pigmented finiss (X) of application, preferably in about 20 DEG C~about 35 DEG C of room temperature) under it is quiet Put (placement) 30 seconds~5 minutes or so.This prevents the 1st coloring films and the mixed layer of the 2nd coloring film.
When being preheated, which usually can be by drying oven being in about 50 DEG C~about 110 DEG C, preferably locating The coated article about 1 minute~30 minutes of institute's application is directly or indirectly heated at a temperature of about 60 DEG C~about 80 DEG C to carry out.
It in addition, usually can be by by room temperature or being heated to about 25 DEG C~about 80 DEG C of the air blown of temperature and arriving coated article Above-mentioned air blast is carried out on application face.
Aqueous 2nd pigmented finiss (Y)
As aqueous 2nd pigmented finiss (Y) used in the present invention, such as it can use and lead in the application of car body Pigmented finiss known per se used in often.
Aqueous 2nd pigmented finiss (Y) usually can be aqueous by the way that the mixing such as matrix resin, crosslinking agent and pigment are dispersed in It is prepared in medium.
As matrix resin, such as it is preferable to use the resins containing carboxyl and hydroxyl.It, can be with as the species of matrix resin It enumerates：Acrylic resin, polyester resin, polyether resin, polycarbonate resin, polyurethane resin etc..
It is preferred that the carboxyl in the resin containing carboxyl and hydroxyl is neutralized.The neutralization with crosslinking agent etc. preferably before mixing It is carried out using alkaline matter.
As the alkaline matter for neutralization, for example,：Ammonia；Ethamine, propylamine, butylamine, benzylamine, monoethanolamine, The primary monoamines such as neopentyl alcohol amine, 2- aminopropanols, 3- aminopropanols；Diethylamine, diethanol amine, two are just or diisopropanolamine (DIPA), N- first The secondary monoamines such as ethylethanolamine, N- ehtylethanolamines；N, N- dimethylethanolamine, trimethylamine, triethylamine, tri-isopropyl amine, methyl two The tertiary monoaminess such as ethanolamine；The polyamines such as Diethylenetriamine, Hydroxy-ethylamino ethamine, ethylamino ethamine, methylaminopropylamine, these Can individually using or two or more is applied in combination.
On the basis of containing the carboxyl in carboxyl and hydroxy resin, the usage amount for the alkaline matter of neutralization generally preferably exists In the range of the equivalent of 0.1 equivalent~1.5, particularly preferably in the range of the equivalent of 0.3 equivalent~1.2.
Consider from viewpoints such as water dispersibles, matrix resin generally preferably has the model in 10mgKOH/g~150mgKOH/g Acid value, the particularly preferred acid value having in the range of 30mgKOH/g~100mgKOH/g in enclosing.In addition, from curability etc. Viewpoint considers that the generally preferable hydroxyl value having in the range of 10mgKOH/g~150mgKOH/g of matrix resin particularly preferably has There is the hydroxyl value in the range of 30mgKOH/g~100mgKOH/g.
And then consider from viewpoints such as weatherability, when matrix resin is acrylic resin, it is usually preferred to have 3000~ Number-average molecular weight, the particularly preferred number-average molecular weight having in the range of 5000~50000 in the range of 100000, and When matrix resin is polyester resin, it is usually preferred to which there is number-average molecular weight in the range of 500~50000, particularly preferably With the number-average molecular weight in the range of 3000~30000.
In the case where using the acrylic resin containing carboxyl and hydroxyl as matrix resin, it can also use to work as to exist and divide The acrylic resin containing carboxyl and hydroxyl manufactured in the case of dispersion stabilizer by emulsion polymerization.
In the case of the acrylic resin manufactured above by emulsion polymerization, it is usually preferred to have more than 100000 The acrylic resin of number-average molecular weight, third particularly preferably with the number-average molecular weight in the range of 200000~2000000 Olefin(e) acid resin.
As the dispersion stabilizer used in emulsion polymerization, except ionic species surfactant or anionic species surface-active Beyond agent, it is 10mgKOH/g~150mgKOH/g or so that can also be suitble to using acid value and number-average molecular weight is 5000~30000 left The water-base resins such as right acrylic resin.
Emulsion polymerization can be carried out by method known per se.
As matrix resin, wherein, pass through the multistage polymerization legal system using carboxylic unsaturated monomer as copolymer composition The acrylic emulsion made can obtain excellent aqueous 2nd pigmented finiss (Y) of painting operation, therefore it is preferred that.That is, make first With not containing or be practically free of (usually in whole monomers be below 3 mass %) carboxylic unsaturated monomer completely The monomer mixture of composition carries out polymerisation, then using containing (being the matter of 5 mass %~30 usually in whole monomers Measure %) monomer mixture of the composition of carboxylic unsaturated monomer carries out polymerisation, acrylic emulsion is thus obtained, this third Olefin(e) acid lotion by using the neutralization of alkaline matter there is viscosity to show (Nian Development Now) effect, it can obtain the paintings such as sag resistance Excellent aqueous 2nd pigmented finiss (Y) of dress workability, therefore it is preferred that.
As crosslinking agent, can use selected from such as melmac, blocked polyisocyanate compound, water dispersible Blocked polyisocyanate compound etc. can with it is at least one kind of in the crosslinking agent of hydroxyl reaction.
The mixing ratio of matrix resin in aqueous 2nd pigmented finiss (Y) and crosslinking agent with total solid of two-component into On the basis of component, matrix resin be preferably generally the mass % of 60 mass %~100 in the range of, particularly preferably 65 mass %~ It in the range of 95 mass %, is further particularly preferably in the range of the mass % of 70 mass %~90, crosslinking agent is preferably generally 0 In the range of the mass % of quality %~40, in the range of the mass % of particularly preferably 5 mass %~35, further it is particularly preferably In the range of the mass % of 10 mass %~30.
It as pigment, is not particularly limited, such as coloring pigment, constitution using inorganic and organic pigment can be suitble to Pigment and bright pigment etc..As above-mentioned coloring pigment, for example,：Titanium oxide, zinc white, carbon black, cadmium red, chrome vermillion, Chrome yellow, chromium oxide, Prussian blue, cobalt blue, azo pigments, phthalocyanine color, quinacridone pigment, isoindoline pigment, intellectual circle system Pigment, pigment etc..As above-mentioned extender pigment, can enumerate：Talcum, clay, kaolin, barium monoxide, barium sulfate, carbonic acid Barium, calcium carbonate, silica and aluminium oxide are white etc..As above-mentioned bright pigment, can enumerate：Aluminium powder, mica powder, With titanium coated mica powder of oxidation etc..
On the basis of the solid constituent of matrix resin and crosslinking agent adds up to, the use level of pigment usually 0.1 mass %~ In the range of 200 mass %, particularly preferably in the range of the mass % of 1 mass %~100.
It can be optionally further suitably using curing catalysts, dispersant, anti-settling in aqueous 2nd pigmented finiss (Y) Agent, antifoaming agent, thickener, ultra-violet absorber, light stabilizer, surface conditioner, antioxidant etc..
The mass % of nonvolatile component concentration generally preferable 15 mass % of aqueous 2nd pigmented finiss (Y) in application~65, Its independent film can be the film of opaque or transparent three-dimensional tone or metal tone.In the present specification, it is opaque Film refers to the film that the light transmittance in 20 μm of cured coating film of independent coating film is less than 5%, and transparent coating refers to 20 μm Above-mentioned cured coating film in film of the light transmittance more than 5%.
Aqueous 2nd pigmented finiss (Y) such as can by aerial spraying, airless spraying, rotary-atomizing application and optionally Ground applies electrostatic makes the film thickness based on cured coating film be typically 5 μm~30 μm to carry out application, particularly 10 μm~25 μm.
In the present invention, aqueous 2nd pigmented finiss (Y) of application on film is coloured the 1st, then transparent paint coating (Z), It but can also be in obtained 2nd coloring of Optional the 2nd pigmented finiss (Y) aqueous to application of transparent paint coating (Z) Film carries out predrying at a temperature of 50 DEG C~100 DEG C or so.
By the predrying, the volatile ingredient in the 2nd coloring film can be made to volatilize to a certain extent.
By above-mentioned predrying, film dry solidification to a certain extent, therefore, when the application on the 2nd coloring film During clear dope (Z), even if the infiltrations such as solvent contained in the film or low-molecular-weight resin ingredient diffuse to the 2nd coloring film In, also can inhibit the viscosity of the 2nd coloring film reduces, and bright pigment when can inhibit using bright pigment etc. etc. is again Flowing thus prevents and generates metallic dot etc..
Particularly, method of forming layered coating film of the invention is in the case where forming high white pearlescent tone multilayer film, The white substrate coating containing white pigment of the 2nd pigmented finiss (Y) can be used as by application successively and containing mica powder Pearly-lustre color base primer is interfered to carry out.It, can be without predrying or 50 DEG C~100 after the application white substrate coating DEG C or so at a temperature of carry out predrying, can also be sintered at a temperature of 100 DEG C~140 DEG C or so.
Process (3)
Clear dope (Z) is coated on the aqueous 2nd coloring film as above formed by aqueous 2nd pigmented finiss (Y).
Clear dope (Z)
As clear dope, such as can be used containing resin components and organic solvent or water etc. such as matrix resin, crosslinking agents And further coordinate curing catalysts, ultra-violet absorber, light stabilizer, apply face regulator, rheology control agent, antioxidant, The organic solvent system or water-based Thermocurable coating that the additive for coatings such as antifoaming agent, wax form, and it has and can pass through The transparency of the lower coating film degree of transparent coating identification formed.
As above-mentioned matrix resin, for example,：At least 1 containing hydroxyl, carboxyl, silanol group, epoxy group etc. The trees such as acrylic resin, polyester resin, alkyd resin, fluororesin, urethane resin, the containing silicone resin of reactive functional groups of kind Fat, particularly preferred hydroxy acryl acid resin.
Hydroxy acryl acid resin (K)
Hydroxy acryl acid resin (K) can make by using conventional method by (k1) hydroxyl polymerism unsaturated monomer and (k2) monomer component that other polymerism unsaturated monomers are formed is copolymerized to manufacture.
Hydroxyl polymerism unsaturated monomer (k1) is that have 1 hydroxyl and 1 polymerism unsaturated bond in 1 molecule Compound.
As hydroxyl polymerism unsaturated monomer (k1), can enumerate：Polymerism unsaturated monomer containing secondary hydroxyl (k1-1) and the polymerism unsaturated monomer of hydroxyl (not including secondary hydroxyl) (k1-2).
As the polymerism unsaturated monomer (k1-1) containing secondary hydroxyl, for example,：(methyl) acrylic acid 2- hydroxyls The carbon number of the alkyl of ester moieties such as propyl ester, (methyl) acrylic acid 2- hydroxybutyls, (methyl) acrylic acid 3- hydroxybutyls is 2 ~8, it is particularly 3~6, the further particularly 3 or 4 polymerism unsaturated monomer with secondary hydroxyl；(methyl) acrylic acid with Containing epoxy group compound (such as Cardura E10, trade name, the manufacture of Hexion Specialty Chemicals companies, newly Capric acid ethylene oxidic ester) addition product etc..Wherein, particularly from the chipping resistance of obtained multilayer film, adhesion, retouching From the viewpoint of property, weatherability and ethanol petrol resistant, preferred (methyl) acrylic acid 2- hydroxy propyl esters.
Above-mentioned monomer (k1-1) can be used a kind or two or more be applied in combination.
The polymerism unsaturated monomer (k1-2) of hydroxyl (not including secondary hydroxyl) is that have 1 hydroxyl (no in 1 molecule Including secondary hydroxyl) and 1 polymerism unsaturated bond compound.
As the monomer, for example,：(methyl) acrylic acid 2- hydroxy methacrylates, (methyl) acrylic acid 2- hydroxyls third (methyl) acrylic acid such as ester, (methyl) acrylic acid 4- hydroxybutyls and the monoesters compound of the dihydric alcohol of carbon number 2~10 (are not wrapped Include the substance with secondary hydroxyl)；(do not include tool by the way that 6-caprolactone is made to carry out ring-opening polymerization and the hydroxyl monomer of modification Have the substance of secondary hydroxyl) etc..
As the hydroxyl monomer that 6-caprolactone is made to carry out ring-opening polymerization and modification, market sale product can be used, As market sale product, for example,：“Placcel FA-1”、“Placcel FA-2”、“Placcel FA-3”、 “Placcel FA-4”、“Placcel FA-5”、“Placcel FM-1”、“Placcel FM-2”、“Placcel FM-3”、 " Placcel FM-4 ", " Placcel FM-5 " (being that Diacel chemical (strain) is manufactured above, trade name) etc..
Above-mentioned monomer (k1-2) can be used a kind or two or more be applied in combination.
Other polymerism unsaturated monomers (k2) are the monomers beyond above-mentioned hydroxyl polymerism unsaturated monomer (k1), There is the compound of 1 polymerism unsaturated bond specifically in 1 molecule.Unsaturated monomer is enumerated in following (1)~(7) (k2) specific embodiment.
(1) the polymerism unsaturated monomer containing acidic group
Polymerism unsaturated monomer containing acidic group is the change with 1 acidic group and 1 polymerism unsaturated bond in 1 molecule Close object.As the monomer：For example,：(methyl) acrylic acid, crotonic acid, itaconic acid, maleic acid and maleic anhydride etc. Carboxyl group-containing monomer；The monomers containing sulfonic acid such as vinyl sulfonic acid, (methyl) sulfoethyl acrylate；2- (methyl) acryloxy second Base acid phosphoric acid ester, 2- (methyl) acryloxypropyls acid phosphoric acid ester, 2- (methyl) acryloxy -3- chloropropyls are acid Acid phosphatases esters monomers such as phosphate, 2- methaciylyloxyethylphenyl phosphoric acid etc..1 kind or 2 can be used in these monomers Kind or more.
(2) acrylic or methacrylic acid and the carboxylate of the monohydric alcohol of carbon number 1~20
Specifically, can enumerate：(methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, Butyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) third Olefin(e) acid -2- ethylhexyls, (methyl) Isooctyl acrylate monomer, (methyl) acrylic acid Yi Rou Dou Kou base esters, (methyl) stearyl acrylate Base ester, (methyl) acrylic acid iso stearyl ester (Osaka Organic Chemical Industry company manufactures, trade name), (methyl) lauryl Base ester, (methyl) tridecyl acrylate, (methyl) stearyl acrylate base ester, (methyl) tetrahydrofurfuryl acrylate, (first Base) cyclohexyl acrylate, (methyl) isobornyl acrylate.
In the carboxylate of aforesaid propylene acid or methacrylic acid with the monohydric alcohol of carbon number 1~20, from finished appearance Raising and from the viewpoint of having both hardness of film, the polymerization using the alicyclic type hydrocarbon containing carbon number 6~20 can be suitble to Property unsaturated monomer (k2-1).
The representative embodiment of alicyclic type hydrocarbon as carbon number 6~20, can enumerate：Cyclohexyl, cyclooctyl, ring ten Dialkyl group, isobornyl, adamantyl and tricyclodecyl etc..
As the specific embodiment of unsaturated monomer (k2-1), for example,：(methyl) cyclohexyl acrylate, (first Base) acrylic acid -4- methylcyclohexyls methyl esters, (methyl) acrylic acid -4- ethylcyclohexyls methyl esters, (methyl) acrylic acid -4- methoxies Butylcyclohexyl methyl esters, (methyl) t-butylcyclohexyl ester, (methyl) acrylic acid ring monooctyl ester, (methyl) acrylic acid cyclododecane Base ester etc. (methyl) acrylate base ester；(methyl) isobornyl acrylate, (methyl) acrylic acid tricyclodecyl, (methyl) third Olefin(e) acid adamantane esters, (methyl) acrylic acid -3,5- dimethyladamantanes base ester, (methyl) acrylic acid -3- Fourth Rings last of the ten Heavenly stems ester etc. contain There is polymerism unsaturated monomer of bridge alicyclic type hydrocarbon etc..Wherein, the chipping resistance particularly from obtained multilayer film, attachment Property, retouching property, from the viewpoint of weatherability and ethanol petrol resistant, preferred (methyl) isobornyl acrylate.
In the case where using unsaturated monomer (k2-1), mixing ratio preferably with respect to monomer component total amount 20 In the range of the mass % of quality %~45, particularly preferably in the range of the mass % of 30 mass %~40.
(3) the polymerism unsaturated monomer containing alkoxysilyl
Specifically, can enumerate：Vinyltrimethoxysilane, vinyltriethoxysilane, acryloxy second Base trimethoxy silane, methacryloxyethyl trimethoxy silane, acryloxypropyl trimethoxy silane, methyl Acryloxypropyl trimethoxy silane, acryloxypropyl triethoxysilane, three second of methacryloxypropyl Oxysilane, vinyl three ('beta '-methoxy ethyoxyl) silane etc..As the wherein preferably polymerization containing alkoxysilyl Property unsaturated monomer, can enumerate：Vinyltrimethoxysilane, γ-acryloxypropyl trimethoxy silane, γ-first Base acryloxypropyl trimethoxy silane etc..
By regarding the polymerism unsaturated monomer for containing alkoxysilyl as constituent, hydroxyl-removal and isocyanates Beyond the cross-bond of base, also generation passes through the mutual condensation reaction of alkoxysilyl and alkoxysilyl and hydroxyl The cross-bond for reacting and being formed, therefore curability can be improved.
When the polymerism unsaturated monomer of alkoxysilyl will be contained as constituent, compared with monomer component Total amount, mixing ratio is preferably in the range of the mass % of 1 mass %~20, particularly preferably the mass %'s of 1 mass %~10 In the range of.
(4) fragrant same clan vinyl monomer
Specifically, can enumerate：Styrene, α-methylstyrene, vinyltoluene etc..
By regarding aromatic series Type of Collective unsaturated monomer as constituent, the glass transition temperature of obtained resin It improves, in addition can obtain high index of refraction and hydrophobic film, finished appearance can be improved by improving the gloss of film Effect.
Using aromatic series Type of Collective unsaturated monomer as during constituent, compared with the total amount of monomer component, match somebody with somebody Composition and division in a proportion example is preferably in the range of the mass % of 5 mass %~30, particularly preferably in the range of the mass % of 10 mass %~20.
(5) the polymerism unsaturated monomer containing glycidyl
Polymerism unsaturated monomer containing glycidyl is that have 1 glycidyl and 1 polymerization in 1 molecule The compound of property unsaturated bond, specifically, can enumerate：Glycidyl acrylate, glycidyl methacrylate etc..
(6) compound of the nitrogen atom of the unsaturated bond containing polymerism
For example,：Acrylamide, Methacrylamide, dimethacrylamide, N, N- dimethyl propyl propylene Amide, N- butoxy methyl acrylamides, N hydroxymethyl acrylamide, N- methylol methacrylamides, diacetone acrylamide acyl Amine, N, N- dimethyl aminoethyls (methyl) acrylate, vinylpyridine, vinyl imidazole, acrylonitrile, methacrylonitrile Deng.
(7) other vinyl compounds
For example,：Vinyl acetate, vinyl propionate, vinyl chloride, tertiary ethylene carbonate etc..As versatic acid second Enester can be enumerated：As market sale product " VEOVA9 ", " VEOVA 10 " (be trade name above, Japan Epoxy Resin (strain) is manufactured) etc..
As other polymerism unsaturated monomers (k2), can use shown in one kind or two or more above-mentioned (1)~(7) Monomer.
From the viewpoint of the finished appearance of film and curability, the weight average molecular weight of hydroxy acryl acid resin (K) is excellent Elect 5000~18000 as, particularly preferably 8000~15000.
From the viewpoint of the curability of film and finished appearance, the glass transition temperature of hydroxy acryl acid resin (K) Degree is preferably -25 DEG C~20 DEG C, particularly preferably -15 DEG C~10 DEG C.
Here, glass transition temperature (Tg) can be calculated by following equatioies.
1/Tg (° K)=(W1/T1)+(W2/T2)+
Tg (DEG C)=Tg (° K) -273
In various, the weight %, T1, T2 of each monomer used in W1, W2, expression copolymerization, respectively table Show the Tg (° K) of the homopolymer of monomer.In addition, T1, T2, be based on Polymer Hand Book (Second Edition, J.BrandupE.H.Immergut is compiled) obtained value.
In addition, the glass transition temperature (DEG C) when the Tg of the homopolymer of monomer is not known is static glassization transformation temperature Degree, such as using differential scanning calorimeter " DSC-50Q types " (Shimadzu Seisakusho Ltd.'s system, trade name), sample is taken from measuring cup, It is sucked by vacuum after removing solvent completely, heat is measured with scope of 3 DEG C/min of the heating rate at -100 DEG C~+100 DEG C Amount variation, as glass transition temperature.
From the finished appearance for improving film and from the viewpoint of storage period, contain hydroxyl in hydroxy acryl acid resin (K) In base polymerism unsaturated monomer (k1) total amount, preferably comprise the mass %, further preferably 80 mass % of 50 mass %~100~ The polymerism unsaturated monomer (k1-1) containing secondary hydroxyl of 100 mass %.
In addition, from the viewpoint of curability and finished appearance, the hydroxyl value of hydroxy acryl acid resin (K) is 140mgKOH/g~210mgKOH/g, preferably in the range of 160mgKOH/g~200mgKOH/g.
To the mixing ratio of hydroxyl polymerism unsaturated monomer (k1) and other polymerism unsaturated monomers (k2) For, from the finished appearance of curability and cured coating film from the viewpoint of, compared with total monomer amount, hydroxyl polymerism is unsaturated Monomer (k1) is preferably mass % of 20 mass %~50 or so, mass % of further preferably 30 mass %~45 or so, other Unsaturated monomer (k2) be preferably mass % of 50 mass %~80 or so, further preferably 55 mass %~70 mass % are left It is right.
From the finished appearance for improving film and from the viewpoint of storage period, the polymerism unsaturated monomer (k1- containing secondary hydroxyl 1) the mass % of 10 mass %~50 is preferably comprised in the monomer total amount in hydroxy acryl acid resin (K), further preferably 20 The mass % of quality %~45.
In addition, from the viewpoint of the curability of coating composition, the acid value of hydroxy acryl acid resin (K) is preferably 0.5mgKOH/g~30mgKOH/g or so, particularly preferably 1mgKOH/g~20mgKOH/g or so.
The monomer mixture being made of above-mentioned polymerism unsaturated monomer (k1) and (k2) can be copolymerized and obtained containing hydroxyl Base acrylic resin (K).
On the basis of the resin solid content quality total amount in clear dope (Z), hydroxy acryl acid resin (K) preferably exists In the range of the mass % of 30 mass %~70, more preferably in the range of the mass % of 35 mass %~65.
It obtains the copolymerization process of hydroxy acryl acid resin (K) for above-mentioned monomer mixture to be copolymerized and does not limit especially It is fixed, copolymerization process known per se can be used, wherein, it can be adapted for use in organic solvent in the presence of polymerization initiator The solution polymerization process being polymerize.
Used organic solvent during as above-mentioned solution polymerization process, for example,：Toluene, dimethylbenzene, Swasol The fragrant same clan solvents such as 1000 (Cosmo oil companies manufacture, trade name, high point petroleum series solvent)；Ethyl acetate, acetic acid fourth The esters solvents such as ester, acetic acid -3- methoxybutyls, ethyl cellosolve acetate, propylene glycol methyl ether acetate；Methyl ethyl ketone, The ketones solvents such as methyl iso-butyl ketone (MIBK), methyl amyl ketone；Propyl propionate, butyl propionate, ethoxyethyl propionate etc..
Can using a kind or two or more singly be applied in combination in these organic solvents, but from the deliquescent side of acrylic resin Face considers that it is preferable to use high boiling esters solvent, ketones solvents.Height boiling alternatively, it is also possible to be further adapted for is applied in combination Fragrant same clan's solvent of point.
As the polymerization initiator that can be used in the copolymerization of hydroxy acryl acid resin (K), for example,：2, 2 '-azobis isobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, two t-amyl peroxy compounds, the tertiary fourth of Peroxycaprylic acid The radical polymerization initiators known per se such as ester, 2,2 '-azo double (2- methylbutyronitriles).
Hydroxy acryl acid resin (K) can be used alone or use two or more simultaneously.
Clear dope (Z) used in the present invention can also use optionally together hydroxy acryl acid resin (K) with Outer resin.Specifically, for example,：Acrylic resin, polyester resin beyond hydroxy acryl acid resin (K), Polyether resin, polyurethane resin, polycarbonate resin etc..Wherein, particularly from the chipping resistance of obtained film, adhesion, From the aspect of retouching property, weatherability and ethanol petrol resistant, as preferred resin, it can enumerate：Hydroxyl polyester tree Fat (L1), hydroxyl polycarbonate resin (L2) and hydroxyl polycarbonate polyester resin (L3).
Hydroxyl group containing polyester resin (L1)
Hydroxyl group containing polyester resin (L1) can by conventional method, for example be made by the esterification of polyacid and polyalcohol It makes.The polyacid is the compound for having in 1 molecule 2 or more carboxyls, for example,：Phthalic acid, isophthalic two Formic acid, terephthalic acid (TPA), succinic acid, adipic acid, azelaic acid, decanedioic acid, tetrahydrophthalic acid, hexahydrophthalic acid, horse Come sour, fumaric acid, itaconic acid, trimellitic acid, Pyromellitic Acid and their acid anhydrides etc., in addition, the polyalcohol is in 1 molecule In there is the compounds of 2 or more hydroxyls, for example,：Ethylene glycol, propylene glycol, 1,3- propylene glycol, 1,4- butanediols, 1, 5- pentanediols, 1,6-HD, 2,2- diethyl -1,3- propylene glycol, neopentyl glycol, 1,9- nonanediols, 1,4- cyclohexanediols, hydroxyl Base pivalic acid neopentyl glycol ester, 2-butyl-2-ethyl-1,3-propanediol, 3- methyl-1s, 5- pentanediols, 2,2,4- trimethyls penta Glycol, hydrogenated bisphenol A etc. and glycols；It is more than the ternarys such as trimethylolpropane, trimethylolethane, glycerine, pentaerythrite Polyol component；And 2,2- dihydromethyl propionic acids, 2,2- dimethylolpropionic acids, 2,2- dihydroxymethyls valeric acid, 2,2- dihydroxy first Hydroxycarboxylic acids such as base caproic acid, 2,2- dihydroxymethyl octanoic acids etc..
Furthermore it is possible to make the alpha-olefins such as propylene oxide and epoxy butane epoxides, " Cardura E10 " (Japan Epoxy Resin companies manufacture, trade name, synthesize highly -branched saturated fatty acid ethylene oxidic ester) etc. mono-epoxy compounds with Acid reacts and these compounds is directed in polyester resin.
To polyester resin import carboxyl when, such as can also by hydroxyl polyester add acid anhydrides carry out it is half-esterification come It imports.
It is examined in terms of the chipping resistance of obtained film, adhesion, retouching property, weatherability and ethanol petrol resistant Consider, hydroxyl group containing polyester resin (L1) is preferably straight-chain.From this side considerations, as above-mentioned polyacid, preferably adipic acid, as Above-mentioned polyalcohol, preferably ethylene glycol, propylene glycol, 1,3-PD, 1,4-butanediol, 1,5-PD, 1,6- hexylene glycols.
The hydroxyl value of hydroxyl group containing polyester resin (L1) is preferably in the range of 85~250mgKOH/g, further preferably 100 In the range of~220mgKOH/g.The number-average molecular weight of hydroxyl group containing polyester resin (L1) preferably in the range of 500~2500, into One step is preferably in the range of 800~2000.
Hydroxyl polycarbonate resin (L2)
Hydroxyl polycarbonate resin (L2) is the makrolon that 2 or more carbonate groups and hydroxyl are respectively provided in molecule Resin.
Hydroxyl polycarbonate resin (L2) be can by according to conventional method make well known polyalcohol and carbonyl agent into Compound obtained from row polycondensation reaction.
As the polyalcohol of the raw material as hydroxyl polycarbonate resin (L2), can enumerate：Glycol and 3 yuan or more Alcohol.
In the polyalcohol as the raw material of hydroxyl polycarbonate resin (L2), as glycol, it can enumerate：1,3- third Glycol, 1,4- butanediols, 1,5- pentanediols, 1,6-HD, 1,7- heptandiols, 1,8- ethohexadiols, 1,9- nonanediols and 1, The branched aliphatic category glycol such as 10- decanediols；2- methyl-1s, 3- propane diols, 3- methyl-1s, 5- pentanediols, neopentyl glycol, 2- ethyls -1,6-HD, 2,2- diethyl -1,3- propylene glycol, 2-butyl-2-ethyl-1,3-propanediol, 2- methyl-1s, 8- The branched aliphatic category glycol such as ethohexadiol, 2,2,4- trimethyl -1,3- pentanediols, 2- ethyl 1,3- hexylene glycols；1,3- hexamethylenes The ester ring types class glycol such as alkane glycol, 1,4- cyclohexane diols, 1,4 cyclohexane dimethanol；Paraxylene glycol, to tetrachloro diformazan The fragrance such as Benzenediol same clan glycol；Ethers glycol such as diethylene glycol, dipropylene glycol etc..These glycol, which may be used alone or in combination, to be made Use two or more.
In the polyalcohol as the raw material of hydroxyl polycarbonate resin (L2), as alcohol more than ternary, Ke Yiju Go out：Glycerine, trimethylolethane, trimethylolpropane, the dimer of trimethylolpropane, pentaerythrite etc..These ternarys with On alcohol may be used alone or in combination and use two or more.
As the carbonyl agent of the raw material as hydroxyl polycarbonate resin (L2), well known carbonyl agent can be used. Specifically, for example,：Alkylene carbonates, dialkyl carbonate, diaryl carbonate, phosgene etc., can be used it 1 kind or two or more is applied in combination.As wherein preferred carbonyl agent, can enumerate：Ethylene carbonate, polypropylene carbonate Ester, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, diphenyl carbonate etc..
From the aspect of chipping resistance, adhesion, retouching property, weatherability and ethanol petrol resistant, the poly- carbon of hydroxyl Acid ester resin (L2) preferably comprises the hydroxyl polycarbonate resin that hydroxyl is 2 and (below, is sometimes referred to as " polycarbonate glycol (L2-1)”)。
Above-mentioned polycarbonate glycol (L2-1) can only be closed without using polyalcohols such as 3 yuan or more of alcohol by using glycol Into as the polyalcohol reacted with above-mentioned carbonyl agent.
As the diol component of polycarbonate glycol (L2-1), usually usable carbon number more than 6, preferably carbon number 6~20, more preferable carbon number 6~15, the glycol of further preferred carbon number 6~12.
As the glycol of carbon number more than 6, can enumerate：Ring alkylidene with carbon number more than 6 it is alicyclic Class glycol and with carbon number more than 6 alkylidene aliphatic category glycol.
As the alicyclic ring same clan glycol of the ring alkylidene with carbon number more than 6, can enumerate：1,3- cyclohexanediols, 1,4- cyclohexanediols, 1,4 cyclohexane dimethanol etc. are as the carbon number more than 6 of glycol entirety, preferably carbon number 6~12 Alicyclic diol.
In above-mentioned, from the viewpoint of chipping resistance, preferred 1,4-CHDM.
As the aliphatic category glycol of the alkylidene with carbon number more than 6, can enumerate：1,6-HD, 1,7- The straight-chains aliphatic category glycol such as heptandiol, 1,8- ethohexadiols, 1,9- nonanediols and 1,10- decanediols；3- methyl-1s, 5- penta Glycol, 2- ethyls -1,6-HD, 2,2- diethyl -1,3- propylene glycol, 2-butyl-2-ethyl-1,3-propanediol, 2- methyl - The carbon such as the branched aliphatic category glycol such as 1,8- ethohexadiols, 2,2,4- trimethyl -1,3- pentanediols, 2- ethyl -1,3- hexylene glycols The aliphatic category glycol of atomicity more than 6, the preferably straight-chain of carbon number 6~10 or branched.
Above-mentioned straight-chain aliphatic category glycol and the aliphatic category glycol of branched can use one of they, also may be used The two is applied in combination.
In above-mentioned, from the viewpoint of chipping resistance, preferred straight-chain aliphatic category glycol, particularly preferred 1,6- oneself two Alcohol.
Consider from viewpoints such as the impact resistances under chipping resistance, low temperature, the number of above-mentioned hydroxyl polycarbonate resin (L2) Average molecular weight is preferably 500~2500, further preferably 800~2000.
As the market sale product of (L2), can enumerate：UM-90, UH-100, UH-200, UC-100 (trade name, space portion Xing Chan companies manufacture) etc..
Hydroxyl polycarbonate polyester resin (L3)
From the viewpoint of impact resistance under from low temperature, hydroxyl polycarbonate polyester resin (L3) is more preferably used.
Hydroxyl polycarbonate polyester resin (L3) for example can make above-mentioned polycarbonate polyester by using known method (L2) react to manufacture with cyclic ester compounds.
As cyclic ester compounds, for example,：δ-valerolactone, 6-caprolactone, ζ-heptalactone, η-caprylolactone, γ- Valerolactone, δ-caprolactone, ε-heptalactone, ξ-caprylolactone, Beta-methyl-gamma-valerolactone, particularly preferably 6-caprolactone.
Consider from viewpoints such as the impact resistances under chipping resistance, low temperature, above-mentioned hydroxyl polycarbonate polyester resin (L3) Number-average molecular weight be preferably 500~2500, further preferably 800~2000.
Hydroxyl group containing polyester resin (L1), hydroxyl polycarbonate resin (L2) and hydroxyl polycarbonate polyester resin (L3) total amount preferably with respect to hydroxy acryl acid resin (K) solid constituent total amount below 100 mass %, more preferably In the range of the mass % of 10 mass %~50.
As the above-mentioned crosslinking agent of clear dope, can enumerate：With can be with the above-mentioned functional group reactions of matrix resin The melmacs of reactive functional groups, urea resin, (sealing end) polyisocyanate compounds, epoxide, containing carboxyl Compound, acid anhydrides, compound containing alkoxysilane group etc., particularly preferred polyisocyanate compounds (PI).
Polyisocyanate compounds (PI)
Polyisocyanate compounds (PI) are the compounds for having in 1 molecule 2 or more isocyanate group.As poly- different Cyanate esters (PI), can enumerate：As polyurethane manufacture with well known compound, such as aliphatic polymeric isocyanate, Alicyclic polymeric isocyanate, aromatic-aliphatic polyisocyanate, aromatic poly-isocyanate and these polyisocyanate are spread out Biology etc..
As aliphatic polymeric isocyanate, specifically, for example,：Trimethylene diisocyanate, four methylenes Base -1,4- diisocyanate, pentamethylene -1,5- diisocyanate, hexamethylene diisocyanate, two isocyanide of 1,2- propylidene Acid esters, 1,2- tetramethylene diisocyanates, 2,3- tetramethylene diisocyanates, 1,3- tetramethylene diisocyanates, 2,2,4- tri- Methyl-hexa-methylene -1,6- diisocyanate, 2,6- diisocyanates root close the fat such as methyl caproate, lysine diisocyanate (cyclo) aliphatic diisocyanates；Lysine ester triisocyanate, tri- isocyanato- octanes of 1,4,8-, tri- isocyanos of 1,6,11- are puted the palms together before one One alkane, 1,8- diisocyanate root conjunction -4- isocyanatomethyls octane, tri- isocyanato- hexanes of 1,3,6-, 2,5,7- front threes Aliphatic triisocyanates such as base -1,8- diisocyanate root conjunction -5- isocyanatomethyl octanes etc..
As above-mentioned alicyclic polymeric isocyanate, for example,：1,3- cyclopentene diisocyanates, 1,4- hexamethylenes Diisocyanate, 1,3- cyclohexane diisocyanates, 3- isocyanatomethyl -3,5,5- trimethylcyclohexylisocyanates (trivial name：Isophorone diisocyanate), 4,4 '-di-2-ethylhexylphosphine oxide (cyclohexyl isocyanate), methyl -2,4- hexamethylenes two it is different Double (isocyanatomethyl) hexamethylene (trivial names of cyanate, methyl -2,6- cyclohexane diisocyanates, 1,3- or 1,4-：Hydrogen Change xylylene diisocyanate) or alicyclic diisocyanates, such as 1 such as its mixture, norbornene alkyl diisocyanate, Tri- isocyanatocyclohexanes of 3,5-, 1,3,5- trimethyls isocyanatocyclohexane, 2- (3- isocyanatopropyls) -2,5- Two (isocyanatomethyls)-bicyclic (2.2.1) heptane, 2- (3- isocyanatopropyls) (isocyanato- first of -2,6- two Base)-bicyclic (2.2.1) heptane, 3- (3- isocyanatopropyls) -2,5- two (isocyanatomethyl)-bicyclic (2.2.1) heptan Alkane, 5- (2- isocyanatoethyls) -2- isocyanatomethyls -3- (3- isocyanatopropyls)-bicyclic (2.2.1) heptan Alkane, 6- (2- isocyanatoethyls) -2- isocyanatomethyls -3- (3- isocyanatopropyls)-bicyclic (2.2.1) heptan Alkane, 5- (2- isocyanatoethyls) -2- isocyanatomethyls -2- (3- isocyanatopropyls)-bicyclic (2.2.1)-heptan Alkane, 6- (2- isocyanatoethyls) -2- isocyanatomethyls -2- (3- isocyanatopropyls)-bicyclic (2.2.1) heptane Etc. alicyclic triisocyanate etc..
As aromatic-aliphatic polyisocyanate, for example,：1,3- or 1,4- xylene diisocyanate or Double (1- isocyanato- -1- the methyl of its mixture, ω, ω '-diisocyanate root conjunction -1,4- diethylbenzenes, 1,3- or 1,4- Ethyl) benzene (trivial name：Tetramethylxylene diisocyanate) or araliphatic diisocyanates such as its mixture, such as Aromatic-aliphatics triisocyanates such as tri- isocyanatomethylbenzenes of 1,3,5- etc..
As aromatic poly-isocyanate, for example,：Metaphenylene diisocyanate, to phenylene diisocyanate Ester, 4,4 '-diphenyl diisocyanate, 1,5- naphthalene diisocyanates, 2,4 '-or 4,4 '-methyl diphenylene diisocyanate or Person its mixture, 2,4- or 2,6- toluene di-isocyanate(TDI)s or its mixture, 4,4 '-toluidine diisocyanate, 4,4 '-two Aromatic diisocyanates, such as triphenyl methanes such as phenylate diisocyanate -4,4 ', 4 " '-triisocyanate, 1,3,5- tri- Aromatic tri-isocyanates, such as 4,4 '-diphenyl methane -2 such as isocyanato- benzene, tri- isocyanato- toluene of 2,4,6-, Aromatic series tetraisocyanate such as 2 ', 5,5 '-tetraisocyanate etc..
In addition, the derivative as polyisocyanate, for example,：The dimerization of above-mentioned polyisocyanate compounds Object, trimer, biuret, allophanate, adduct, carbodiimide, urea diketone, urea imines, isocyanuric acid ester, oxadiazines three Ketone, polymethylene polyphenyl base polyisocyanate (thick MDI, polymeric MDI) and thick TDI etc..
In above-mentioned, the easiness obtained from industry considers, can be particularly suitable for (below having using hexamethylene diisocyanate When referred to as HMDI), isophorone diisocyanate (hereinafter sometimes referred to IPDI) and their derivative.
Above-mentioned polyisocyanate compounds can be used alone or use two or more simultaneously.
The content of polyisocyanate compounds (PI) is preferably with respect to the solid constituent total amount of hydroxy acryl acid resin (K) Below 200 mass %, more preferably in the range of the mass % of 50 mass %~150.
As the curing catalysts of clear dope, can individually using or that two or more is applied in combination is well known solid Change catalyst, such as tin octoate, dibutyl tin acetate, dibutyl two (2 ethyl hexanoic acid) tin, dibutyl tin dilaurate, two Octyl group oxalic acid tin, dioctyl two (2 ethyl hexanoic acid) tin, Dibutyltin oxide, dioctyl tin oxide, dibutyl tin aliphatic acid Salt, dibutyl tin bis-fatty acid salt, 2 ethyl hexanoic acid lead, zinc octoate, zinc naphthenate, fatty acid zinc class, cobalt naphthenate, octanoic acid The organo-metallic compounds such as calcium, copper naphthenate, four (2- ethylhexyls) titanate esters；Tertiary amine etc..
Wherein, preferred organo-metallic catalyst (M).Organo-metallic catalyst (M) is by zinc compound (M-I) and amidine chemical combination The catalyst that object (M-II) is formed.By using zinc compound (M-I) and amidine compound (M-II) simultaneously so that between low-temperature short-time Interior curability is excellent, and the finished appearance of the film formed is good, and can be maintained as the storage period of 2 liquid type coating To a certain degree.
It is thought that because the catalyst being made of zinc compound (M-I) and amidine compound (M-II) forms complex compound knot Structure, amidine compound become end-capping reagent, and the amidine compound as the end-capping reagent dissociates at low temperature, after amidine compound dissociation, zinc impregnation The excellent catalytic performance activation of the curability at low temperatures of object script is closed, can be had both as a result, in the low-temperature short-time of coating composition It curability and can will maintain to a certain degree storage period.
As zinc compound (M-I), for example,：Salts of carboxylic acids compound, acetylacetone,2,4-pentanedione zinc complex etc..Especially Ground can be suitble to use salts of carboxylic acids compound.
As salts of carboxylic acids compound, specifically, following formula (1) compound represented can be enumerated.
(RCO2)nZn (1)
(in formula, R represents alkyl, the aralkyl or alkylaryl of carbon number 1~30 of carbon number 1~30, and n is tool There is the integer of more than 1 and 4 the following values)
More specifically, for example,：It is 2 ethyl hexanoic acid zinc, zinc acetate, zinc octoate, zinc naphthenate, zinc octoate, hard Resin acid zinc, zinc neodecanoate, zinc oleate etc..
It is excellent from catalytic activity and it is industrial obtain readily from the aspect of, can be particularly suitable for using zinc octoate.
Amidine compound (M-II) is with R1- C (=NR2)-NR3R4The organic compound of shown structure.In the structure In, have 1 nitrogen-atoms carbon (C) atom is bonded to double bond and 1 nitrogen-atoms with singly bound in the structure of carbon (C) atom.
In formula R1- C (=NR2)-NR3R4(1) in,
R1It is hydrogen atom, the commutable organic group for being bonded to carbon atom, amino, specifically, can enumerates：It is desirable The alkyl in generation or the hydroxyl that can be etherified.
R2And R3Independence mutually is hydrogen atom or is bonded to the organic group of carbon atom or has structure bonding to each other Heterocycle (is included with the hetero atom of 1 or 2 or more or with the bicyclic of the heteroatomic bonding of 1 or 2 or more).
R4It can enumerate：Hydrogen atom, the commutable organic group for being bonded to carbon atom, the hydroxyl that can be etherified, preferably It enumerates：The alkyl of commutable carbon number more than 8.
In R1Or R4In the case of being organic group, they can be the group or example for example with 1 to 40 carbon atom Polymeric groups such as with 500~50000 molecular weight.
R1、R2、R3、R4Shown group can contain alcohol hydroxyl group as substituent group independently.
As by formula R1- C (=NR2)-NR3R4(1) expression and R2With R3The amidine compound not being bonded, specifically For, it can enumerate：
N '-cyclohexyl-N, N- dimethyl carbonamidine, N '-methyl-N, N- di-n-butyl ethanamidine, N '-octadecyl-N, N- bis- Methylrnethwirnidamide, N '-cyclohexyl-N, N- dimethyl-penten amidine, 1- methyl -2- cyclohexyliminos pyrrolidines, 3- butyl -3,4,5,6- Tetrahydropyrimidine, N- (hexyl iminomethyl) morpholine, N- (α-(decyl Iminoethyl) ethyl) pyrrolidines, N '-decyl-N, N- Dimethyl carbonamidine, N '-decyl-N, N- dimethyl carbonamidine, N '-cyclohexyl-N, N- ethanamidine etc..
In addition, as the amidine compound, there is R2-R3Include 5 to 7 yuan of rings of 2 nitrogen-atoms in amidine structure, and R1- R3Or R1-R4In 1 pass through the amidine chemical combination that 1 nitrogen-atoms in amidine structure and multiple carbon atoms form the structure of 5 to 9 yuan of rings Object is also contained in amidine compound (M-II).
As the amidine compound having a structure in which, specifically, can enumerate：1,5- diazabicyclos (4.3.0) Ketone -5- alkene, 11 carbon -7- alkene of 1,8- diazabicyclos (5.4.0), 1,4- diazabicyclos (3.3.0) octyl- 4- alkene, 2- methyl - 1,5- diazabicyclos (4.3.0) ketone -5- alkene, 2,7,8- trimethyl -1,5- diazabicyclos (4.3.0) ketone -5- alkene, 2- fourths Base -1,5- diazabicyclos (4.3.0) ketone -5- alkene, 13 carbon -8- alkene of 1,9- diazabicyclos (6.5.0) etc..
In addition, as amidine compound, can enumerate：With formula R1- C (=NR2)-NR3R4(1) R in2With R3It is bonded heterocyclic compound, such as imidazoline, imidazoles, tetrahydropyrimidine, dihydro-pyrimidin, the pyrimidine of the structure formed.
Imdazole derivatives are usually represented by following structural formula.
[chemical formula 14]
In above-mentioned, as R5、R6、R7And R8, it is each independent mutually, it can enumerate：Hydrogen atom, alkyl or substitution alkyl, hydroxyl Alkyl, pi-allyl, aralkyl, cycloalkyl, heterocycle, ether, thioether, halogen ,-N (R)2, polyethylene polyamines, nitro, ketone group, ester group, Carbon acylamino and the alkyl substituent of these functional groups.
As imidazolium compounds, specifically, can enumerate：N- (2- ethoxys) imidazoles, N- (3- aminopropyls) imidazoles, 4- (methylol) imidazoles, 1- (tert-butoxycarbonyl) imidazoles, imidazoles -4- propionic acid, 4- carboxyls imidazoles, 1- butyl imidazoles, 1- methyl Imidazoles, 2- methyl -4- imidazolyl carboxylic acids, 4- formyl imidazoles, 1- (ethoxy carbonyl) imidazoles, propylene oxide and imidazoles and 2- first The reactant of base imidazoles, 1- trimethyl-silyl-imidazoles, 4- (methylol) imidazole hydrochloride, the chloro- 2,3- propylene oxide of 1- with Copolymer, 1- (p-toluenesulfonyl) imidazoles, 1,1- carbonyldiimidazoles, 1- (2- cyano ethyls) -2- ethyl -4- methyl of imidazoles Imidazoles, 2- phenyl -2- imidazolines pyromellitic ester, 4- (methylol) imidazoles picrate, 2- acrylic acid and 4,5- dihydro -2- nonyls Disodium salt, 1- (cyano ethyl) -2- 11 of base -1H- imidazoles -1- ethyl alcohol and 2- heptyl -4,5- dihydro -1H- imidazoles -1- ethyl alcohol Formic acid esters, imidazole natrium, the imidazoles silver etc. of alkyl imidazole trimellitate, 1- (2- hydroxypropyls) imidazoles.
Above-mentioned amidine compound can be used alone or use two or more simultaneously.
Specifically, in the present invention, organo-metallic catalyst (M) is zinc complex, which for example can be by by 1 Mole zinc polycarboxylate and 2 moles of amidine compound heated to manufacture in methanol equal solvent.
In above-mentioned manufacture, by keep at about 50 DEG C about 2 it is small when until making zinc as transparent solution state Complex compound.Filter the clear solution and drying.
The molar ratio of amidine compound (M-II) and zinc compound (M-I) be (molal quantity of the molal quantity of (M-II)/(M-I) Value) be preferably 1.3~8.0 scope, particularly preferably 1.6~5.0 scope, further particularly preferably 1.8~4.0 model It encloses.
If above-mentioned molar ratio is outside 1.3~8.0 scope, curability, storage period and finished product between low-temperature short-time sometimes Appearance becomes inadequate.
From the viewpoint of curability, storage period and finished appearance between low-temperature short-time, compared with (K) ingredient, it is selected from (L1) at least one kind of, (PI) ingredient the total amount in ingredient, (L2) ingredient and (L3) ingredient, the amount of (M) ingredient is preferably 0.05 In the range of the mass % of quality %~5, particularly preferably in the range of the mass % of 0.1 mass %~4, further particularly preferably exist In the range of the mass % of 0.3 mass %~3.If less than 0.05 mass %, then curability becomes not fill between low-temperature short-time sometimes Point.In addition, if more than 5 mass %, then the finished appearance of the film obtained sometimes becomes inadequate.
Organo-metallic catalyst (M) is also dissolvable in water solvent and uses.Solvent is not particularly limited, for example,： The alcohols such as ethylene glycol, diethylene glycol, dipropylene glycol, propylene glycol, butanediol, toluene, dimethylbenzene, mineral turpentine, mineral spirits Wait esters, methyl ethyl ketone, the methyl tert-butyls such as hydro carbons, ethyl acetate, butyl acetate, ethylene glycol methyl acetate, cellosolve acetate The gylcol ethers such as the ketones such as base ketone, cyclohexanone, 3- ethoxyl ethyl propionates, 3- methoxyacetic acid butyl esters；N, N- dimethyl methyl The organic solvent equal solvent of the amides such as amide, DMAC N,N' dimethyl acetamide.
It,, can also basis in addition to organo-metallic catalyst (M) as catalyst in the coating composition of the present invention It needs using the catalyst beyond organo-metallic catalyst (M).
It is not particularly limited as the catalyst beyond above-mentioned organo-metallic catalyst (M), as long as polyurethane The conventionally known organic metal with catalyst is made, specifically, can be enumerated：Oxalic acid tin, two tin octoates, two oleic acid Tin, tin dilaurate tin, Dibutyltin oxide, dibutyltin diacetate, dibutyl tin laurate, dibutyl tin dichloride, two The organotin catalysts such as dioctyltin laurate.Wherein, preferably two tin octoates, dibutyl tin laurate.
End-capping reagent (N)
End-capping reagent (N) used in clear dope is selected from beta-diketon class, beta-keto acid esters, malonic acid esters, β tools There is at least one kind of compound in the ketone of hydroxyl, esters of the β aldehydes and β with hydroxyl with hydroxyl.
Specifically, for example,：Beta-diketon class：Acetylacetone,2,4-pentanedione, benzoyl, dibenzoyl methane, beta-ketoester Class：Ethyl methyl esters, ethyl acetoacetate, ethyl benzoylacetate, malonic acid esters：Malonic ester, β have hydroxyl Ketone：Diacetone alcohol, the β aldehydes with hydroxyl：Salicylide, the β esters with hydroxyl：Gaultherolin etc..
In above-mentioned, particularly from the aspect of extended pot life effect height, preferred beta-diketon class, particularly preferred levulinic Ketone.
Compared with K) it is ingredient, at least one kind of, (PI) ingredient in (L1) ingredient, (L2) ingredient and (L3) ingredient Solid constituent total amount, the amount of end-capping reagent (N) are the mass % of 0.7 mass %~25, are preferably the mass % of 1.0 mass %~20, into One step is preferably the mass % of 2.0 mass %~15.
The amount of end-capping reagent (N) is compared with K) ingredient, at least 1 in (L1) ingredient, (L2) ingredient and (L3) ingredient Kind, (PI) are if the solid constituent total amount of ingredient is less than 0.7 mass %, and extended pot life effect becomes inadequate sometimes, such as Fruit is more than 25 mass %, then extended pot life effect culminates, in addition, the curability of the film obtained sometimes becomes not fill Point.
As above-mentioned ultra-violet absorber, conventionally known ultra-violet absorber can be used, for example,：Benzo three The ultra-violet absorbers such as azoles system absorbent, triazine system absorbent, salicyclic acid derivatives system absorbent, benzophenone series absorbent.
As the content in the clear dope (Z) of ultra-violet absorber, from the viewpoint of weatherability, yellowing resistance, lead to Often compared with resin solid content total amount, preferably in the range of the mass % of 0 mass %~10, particularly preferably in 0.2 mass % In the range of~5 mass %, further particularly preferably in the range of the mass % of 0.3 mass %~2.
As above-mentioned light stabilizer, conventionally known light stabilizer can be used, for example,：Hindered amines light is stablized Agent.
As the content in the clear dope (Z) of light stabilizer, from the viewpoint of weatherability, yellowing resistance, usual phase It is preferably the mass % of 0 mass %~10 for resin solid content total amount, the mass % of particularly preferably 0.2 mass %~5, into One step is particularly preferably in the range of the mass % of 0.3 mass %~2.
In one embodiment, clear dope (Z) contains using the resin solid content quality total amount of clear dope as base Hydroxy acryl acid resin (K), the solid constituent compared with hydroxy acryl acid resin (K) of the mass % of 30 mass % of standard~70 Total amount is below 100 mass % selected from hydroxyl group containing polyester resin (L1), hydroxyl polycarbonate resin (L2) and hydroxyl At least one kind of resin in polycarbonate polyester resin (L3) and total compared with the solid constituent of hydroxy acryl acid resin (K) Amount is preferably the polyisocyanate compounds (PI) of below 200 mass %.
In another embodiment, clear dope (Z) contains using the resin solid content quality total amount of clear dope as base The hydroxy acryl acid resin (K) of the mass % of 30 mass % of standard~70；Compared with the solid constituent of hydroxy acryl acid resin (K) Total amount is below 100 mass % selected from hydroxyl group containing polyester resin (L1), hydroxyl polycarbonate resin (L2) and hydroxyl At least one kind of resin in polycarbonate polyester resin (L3)；Solid constituent total amount compared with hydroxy acryl acid resin (K) is excellent Elect the polyisocyanate compounds (PI) below 200 mass % as；Compared with (K) ingredient, selected from (L1) ingredient, (L2) ingredient with And the total amount of at least one kind of and (PI) ingredient in (L3) ingredient is the organo-metallic catalyst of the mass % of 0.05 mass %~5 (M)；With compared with (K) ingredient, at least one kind of and (PI) ingredient in (L1) ingredient, (L2) ingredient and (L3) ingredient Solid constituent total amount for the mass % of 0.7 mass %~25 end-capping reagent (N).
Clear dope (Z) used in the present invention can be a liquid type coating or more liquid such as two-liquid type coating Type coating.In the clear dope (Z) in the case where using polyisocyanate compounds (PI) as above-mentioned crosslinking agent, from From the viewpoint of storage stability, host agent by containing above-mentioned matrix resin is preferably formed as and containing above-mentioned polyisocyanate chemical combination The two, is used in mixed way by the two-liquid type coating that the crosslinking agent of object (PI) is formed before the use.
Coating process as clear dope (Z) is not particularly limited, such as can be sprayed by aerial spraying application, without air It applies the coating process such as application, rotary-atomizing application, curtain painting application and forms wet coating.It, can also be optional in these coating process Ground applies electrostatic.Wherein, particularly preferred aerial spraying application.The film thickness of clear dope (Z) is generally preferably calculated with curing film thickness It it is preferably 20~45 μm for 10~50 μm.
In addition, in the case where carrying out aerial spraying application, airless spraying application and rotary-atomizing application, preferably in advance First use organic solvent equal solvent suitable for the viscosity of adjustment clear dope (Z) so that being usual suitable for the range of viscosities of the application The range of viscosities for being 15~60 seconds or so at 20 DEG C in Ford cup #No.4 viscosimeters.
Process (4)
It is made of the 1st coloring film, the 2nd coloring film and transparent coating this 3 coating film formed as described above more Coating film can be heated by the sintering method of common film, such as Hot-blast Heating, infrared heating, high-frequency heating.
From the aspect of excellent curability under from low temperature, heating keeps temperature (holding temperature) to be suitble to 60 DEG C~140 In the range of DEG C, it is particularly suitable in the range of 70 DEG C~120 DEG C.Heated hold time (retention time) be suitble to 10 minutes~ In the range of 50 minutes, it is particularly suitable in the range of 20 minutes~40 minutes.
Before above-mentioned sintering curing is carried out, optionally shape 1 minute~60 minutes or so at room temperature and/or 40 The preheating of 1~60 minute or so is carried out at a temperature of~80 DEG C.
The method of forming layered coating film of the present invention can be formed be respectively provided with compared with metal parts or plastic components it is excellent resistance to Bursting apart property, adhesion, retouching property, the film of weatherability and ethanol petrol resistant.
The present invention can be suitable as the multilayer film side of being formed of whole industrial products containing metal material and plastic material Method.It wherein, can be especially suitable for the method for forming layered coating film of automobile.
By the present invention method of forming layered coating film, can be formed be respectively provided with compared with metal parts or plastic components it is excellent Chipping resistance, adhesion, retouching property, weatherability and ethanol petrol resistant film the reasons why not yet determine, but can be such as Lower supposition.In the method for forming layered coating film of the present invention, aqueous 1st pigmented finiss contains specific waterborne polyurethane resin, Therefore, opposing metallic component or plastic components are respectively provided with excellent adhesion.Thus, thus it is speculated that show excellent chipping resistance and resistance to Ethanol vapor oiliness.In addition, aqueous 1st pigmented finiss contains blocked polyisocyanate, and therefore, low temperature and the curability in the short time It is excellent.In addition, by the excellent curability, the crosslink density of film becomes higher, and therefore, water resistance, adhesion are excellent.And then By the excellent curability, the viscosity of the 1st coloring film is brought to show effect, film is coloured with the 2nd when can inhibit application Mixed layer, can inhibit because mix layer caused by multilayer film finished appearance reduction.In addition, thus it is speculated that more due to what is further obtained The light transmittance of coating film is low, so as to can inhibit because of the deterioration of photogenic film, therefore, can be formed and resistance to burst apart with excellent The film of property, adhesion, wetability, weatherability and ethanol petrol resistant.
Think through these synergies, by the method for forming layered coating film of the present invention, can be formed compared with metal portion Part or plastic components are respectively provided with the film of excellent chipping resistance, adhesion, retouching property, weatherability and ethanol petrol resistant. And then in the multilayer film formed by the method for forming layered coating film of the present invention, the storage period of clear dope can maintain Appropriate length.
Embodiment
Hereinafter, enumerate embodiment and comparative example further specifically describes the present invention.But the present invention is not limited in this A little embodiments.In addition, " part " and " % " is according to quality criteria.In addition, the film thickness of film is based on cured coating film.
The manufacture of aqueous 1st pigmented finiss (X)
The manufacture of chlorine-free polyolefin-based resins (A)
Production Example 1
It will be by the maleation polypropylene resin of weight average molecular weight 80000 (chlorination rate 22%, maleic acid modified amount 2.0%, acid Value 30mgKOH/g) 500 parts, the mixtures of 50 parts of compositions of 150 parts of normal heptane and N-Methyl pyrrolidone be heated to 50 DEG C, add Enter 12 parts of dimethylethanolamine and " NOIGEN EA-140 " (nonionic class surfactant, the manufacture of the 1st industrial pharmaceutical (strain), Trade name) 5 parts, when synthermal lower stirring 1 is small after, be slowly added to 2000 parts of deionized water, further carry out 1 it is small when stir.
Then, depressurized at a temperature of 70 DEG C, be distilled off adding up to 600 portions of normal heptanes and water, obtain solid constituent and contain The chlorine-free vistanex dispersion liquid (A-1) of rate 23.6%.
Production Example 2
In the four-hole boiling flask for being equipped with blender, condenser pipe, thermometer and dropping funel, maleic anhydride is grafted poly- Propylene (compared with the polypropylene that Metallocene-type catalysts is used to obtain, is modified with 4 mass % of maleic acid addition amount and obtained Substance, 80 DEG C of fusing point, Mw about 150,000, Mw/Mn about 2.5) 100g heat melting at 140 DEG C, add polyoxyethylene stearyl base Ether (" Newcol 1820 ", single end hydroxyl polyoxyethylene compound, Japanese emulsifier company manufacture) 15g, while stirring one While it is reacted when progress 4 is small at 140 DEG C.After reaction, 90 DEG C are cooled to, deionized water is added in and is filtered, obtain solid constituent 30% chlorine-free vistanex dispersion liquid (A-2).
The manufacture of waterborne polyurethane resin (B)
Production Example 3
In the reactive tank addition polytetramethylene glycol (number-average molecular weight 1000) for possessing thermometer, mixer, reflux condenser 211.9 parts, α, 11.5 parts of α-dihydromethyl propionic acid, 6.9 parts of trimethylolpropane, 112.2 parts of isophorone diisocyanate with And 298.5 parts of methyl ethyl ketone, after reaction system nitrogen is substituted, make its reaction in 80 DEG C in the state of stirring, obtain The NCO ends urethane prepolymer of free isocyanate group content 3.2%.The obtained methyl ethyl ketone solution is cooled to 40 DEG C, after adding in the deionized water 493.2g emulsifications containing 5.2 parts of triethylamine, 5% ethylenediamine solution 159.2 is added wherein Part, stirring after sixty minutes, is distilled off methyl ethyl ketone under heating under reduced pressure, concentration adjustment is carried out with deionized water, consolidate 15 minutes time, acid value 14mgKOH/g, average grain diameter 120nm needed for body ingredient 35%, the film forming at a temperature of 20 DEG C Waterborne polyurethane resin dispersion liquid (B-1).
Production Example 4~13
In Production Example 3, set as shown in table 1 with being combined into, in addition, by being operated in the same manner as Production Example 3 To each waterborne polyurethane resin dispersion liquid (B-2)~(B-11).
It is represented in addition, the cooperation of table 1 is solid content, (note 1) in table 1 is as shown in following.
The manufacture of (note 1) polyester polyol A
By 49 parts of the sodium salt of 67 parts of polyethylene glycol (number-average molecular weight 300) and 5- dimethyl sulfoisophthalates and two 0.2 part of butyl tin oxide is incorporated in reaction vessel, 190 DEG C is warming up under the decompression state of 5mmHg, one side distillation for removing methanol While ester exchange reaction when progress 6 is small, obtains averagely having 5 sodium sulfonate groups, hydroxyl value 29.6mgKOH/g, number in 1 intramolecular The polyester polyol A of average molecular weight 3700.
[table 1]
Table 1
The manufacture of blocked polyisocyanate compound (C) with nonionic hydrophilic radical
Production Example 14
Possess thermometer, thermostat, agitating device, reflux condenser, nitrogen ingress pipe, Dropping feeder and except solvent letter " Sumidule N-3300 " is added in the reaction vessel of easy grabber, and (trade name is firmly changed the manufacture of Bayer urethanes company, is derived from The polyisocyanate containing isocyanurate structure of hexamethylene diisocyanate, solid constituent about 100%, isocyanate group Containing ratio 21.8%) 1610 parts, " UNIOX M-550 " (You companies manufacture, and polyethylene glycol monomethyl ether, average molecular weight is about 550) 275 parts and 0.9 part of 2,6- di-tert-butyl-4-methy phenol, are sufficiently mixed, under nitrogen stream (Chisso flows down In) in When 130 DEG C of heating 3 are small.Then, 1150 parts of 550 parts of ethyl acetate and Diisopropyl malonate are added in, under nitrogen stream on one side Stirring is while add in 14 parts of 28% methanol solution of sodium methoxide, when stirring 8 is small at 65 DEG C.Isocyanide in obtained resin solution Acid esters amount is about 0.1 mole/kg.3110 parts of 4- methyl -2- amylalcohols are added in wherein, while the temperature of system is maintained at 80 DEG C ~85 DEG C of one side at reduced pressure conditions by 3 it is small when solvent is distilled off, obtain blocked polyisocyanate compound solution (C-1) 4920 parts.Except in the simple grabber of solvent contain 585 parts of isopropanols.Obtained blocked polyisocyanate compound solution (C-1) Solid component concentration be about 60%.
Production Example 15
Possess thermometer, thermostat, agitating device, reflux condenser, nitrogen ingress pipe, Dropping feeder and except solvent letter " Sumidule N-3300 " is added in the reaction vessel of easy grabber, and (trade name is firmly changed the manufacture of Bayer urethanes company, is derived from The polyisocyanate containing isocyanurate structure of hexamethylene diisocyanate, solid constituent about 100%, isocyanate group Containing ratio 21.8%) 1610 parts, " UNIOX M-550 " (manufacture of You companies, polyethylene glycol monomethyl ether, average molecular weight are about 550) 275 points and 0.9 part of 2,6- di-tert-butyl-4-methy phenol, are sufficiently mixed, small in 130 DEG C of heating 3 under nitrogen stream When.Then, 1150 parts of 550 parts of ethyl acetate and Diisopropyl malonate are added in, is stirred under nitrogen stream while adding in 14 parts of 28% methanol solution of sodium methoxide, when stirring 8 is small at 65 DEG C.Amount of isocyanate in obtained resin solution is about 0.1 mole/kg.The solid component concentration of obtained blocked polyisocyanate compound solution (C-2) is about 60%.
Production Example 16
Possess thermometer, thermostat, agitating device, reflux condenser, nitrogen ingress pipe, Dropping feeder and except solvent letter 1610 parts of " Sumidule N-3300 " and 236 parts of hydroxy new pentane acid are added in the reaction vessel of easy grabber, stir while It is sufficiently mixed, under nitrogen stream when 130 DEG C of heating 3 are small.Then, 550 parts of ethyl acetate and Diisopropyl malonate are added in It 930 parts, is stirred under nitrogen stream while 14 parts of 28% methanol solution of sodium methoxide is added in, when stirring 8 is small at 65 DEG C. Amount of isocyanate in obtained resin solution is about 0.1 mole/kg.2530 parts of 4- methyl -2- amylalcohols are added in wherein, on one side By the temperature of system be maintained at 80 DEG C~85 DEG C one side at reduced pressure conditions through 3 it is small when solvent is distilled off, it is poly- different to obtain sealing end 4450 parts of cyanate esters solution (C-3).Except in the simple grabber of solvent contain 475 parts of isopropanols.Obtained sealing end gathers different The solid component concentration of cyanate esters solution (C-3) is about 60%.
Production Example 17
Possess thermometer, thermostat, agitating device, reflux condenser, nitrogen ingress pipe, Dropping feeder and except solvent letter " Sumidule N-3300 " is added in the reaction vessel of easy grabber, and (trade name is firmly changed the manufacture of Bayer urethanes company, is derived from The polyisocyanate containing isocyanurate structure of hexamethylene diisocyanate, solid constituent about 100%, isocyanate group Containing ratio 21.8%) 480 parts, 365 parts of 150 parts of ethyl acetate and Diisopropyl malonate, while stirring under nitrogen stream While 4 parts of 28% methanol solution of sodium methoxide is added in, when stirring 8 is small at 65 DEG C.Isocyanates in obtained resin solution It measures as 0.07 mole/kg.870 parts of 4- methyl -2- amylalcohols are added in wherein, while the temperature of system is maintained at 80 DEG C~85 DEG C On one side at reduced pressure conditions by 3 it is small when solvent is distilled off, add 120 parts of 4- methyl -2- amylalcohols, obtain blocking poly- isocyanide 1400 parts of acid ester composite solution (C-4).Except in the simple grabber of solvent contain 183 parts of isopropanols.The obtained poly- isocyanide of sealing end The solid component concentration of ester compound solution (C-4) is about 60%.
In addition, (C-1) and (C-2) is the blocked polyisocyanate compound solution used in aftermentioned embodiment, (C- 3) and (C-4) is the blocked polyisocyanate compound without nonionic hydrophilic radical used in aftermentioned comparative example Solution.
The manufacture of hydroxy acryl acid resin
Production Example 18
Hold in the reaction for possessing thermometer, thermostat, agitating device, reflux condenser, nitrogen ingress pipe and Dropping feeder In device add in 35 parts of propylene glycol monopropyl ether, after being warming up to 85 DEG C, last 4 it is small when be added dropwise 30 parts of methyl methacrylate, propylene Sour 20 parts of 2- ethylhexyls, 29 parts of n-butyl acrylate, 15 parts of acrylic acid 2- hydroxy methacrylates, 6 parts of acrylic acid, propylene glycol list propyl The mixture of 15 parts of ether and 2.3 parts of 2,2'- azo double (2,4- methyl pentane nitriles), when completion of dropwise addition post curing 1 is small.Then, Last again 1 it is small when 10 parts of propylene glycol monopropyl ether and 2 are added dropwise, the mixture of 1 part of 2 '-azo double (2,4- methyl pentane nitriles) drips When adding end post curing 1 small.7.4 parts of diethanol amine is added, obtains the hydroxy acryl acid resin solution of solid constituent 55% (E-1).The acid value of obtained hydroxy acryl acid resin is 47mgKOH/g, hydroxyl value 72mgKOH/g.
The manufacture of hydroxyl group containing polyester resin
Production Example 19
Oneself is added in the reaction vessel for possessing thermometer, thermostat, agitating device, reflux condenser and separator 192 parts of diacid, 307 parts of hexahydrophthalic anhydride, 439 parts of 2-butyl-2-ethyl-1,3-propanediol, 1,6-HD 88.7 Part and 36.0 parts of trimethylolpropane, last 3 it is small when after 160 DEG C are warming up to 230 DEG C, while being distilled off using separator Condensation water while being maintained at 230 DEG C, makes its reaction until as desired acid value.Inclined benzene three is added in the reaction product 20.2 parts of acid anhydrides after carrying out addition reaction in 30 minutes at 170 DEG C, is cooled to less than 50 DEG C, with 2- (dimethylamino) ethyl alcohol It is neutralized, is slowly added deionized water, thus obtain the hydroxyl group containing polyester resin aqueous dispersions (F- of solid component concentration 45% 1).The acid value of obtained hydroxyl group containing polyester resin is that 20mgKOH/g, hydroxyl value are that 60mgKOH/g, number-average molecular weight are 1,700.
The making of 1st pigmented finiss (X)
Production Example 20
Coordinate chlorine-free vistanex dispersion liquid (A-1) 35 parts of (solid constituent), aqueous polyurethanes according to conventional method Resin dispersion liquid (B-1) 20 parts (solid constituents), the blocked polyisocyanate compound solution with nonionic hydrophilic radical (C-1) 20 parts (solid constituents), hydroxy acryl acid resin solution (E-1) 10 parts (solid constituents), hydroxyl group containing polyester resin (F- 1) (" Ketjen black EC600J ", Lyons AudioCodes help Co., Ltd.'s manufacture, commodity for 15 parts (solid constituents), conductive pigment (D-1) Name, conductive carbon black pigment) 5 parts, 100 parts of " JR-806 " (Tayca companies manufacture, trade name, titanium white) and mix scattered, spend Ionized water dilute so that solid constituent be 20%, obtain aqueous 1st pigmented finiss (X-1).
Production Example 21~42
In Production Example 20, it will be set to as shown in table 2 with being combined into, in addition, by being grasped in the same manner as Production Example 20 Make, obtain each aqueous 1st pigmented finiss (X-2)~(X-23).
It is represented in addition, the cooperation of table 2 is solid constituent, (note 2) in table 2 is as shown in following.
(by maleic acid modified obtained acid value be 35mgKOH/g to (note 2) watersoluble chlorinated polyolefin (A-3) and chlorine contains Rate is the aqueous dispersion of 22% maleic acid modified chlorinated polypropylene)
[table 2]
Table 2
2 (Continued) of table
The manufacture of clear dope (Z)
The manufacture of hydroxy acryl acid resin (K)
Production Example 43~50
Ethoxyethyl propionate is added in the four-hole boiling flask for possessing agitating device, thermometer, condenser pipe, nitrogen inlet 31 parts, 155 DEG C are warming up in the case where nitrogen is ventilated.After reaching 155 DEG C, stop the ventilation of nitrogen, last 4 it is small when be added dropwise by The monomer mixture for the composition cooperation that monomer and polymerization initiator shown in Table 3 below are formed.Then, while leading at 155 DEG C Enter nitrogen while after when curing 2 is small, be cooled to 100 DEG C, be diluted for 32.5 parts with butyl acetate, thus obtain solid constituent 60% hydroxy acryl acid resin (K-1)~(K-8).By the quality solid constituent concentration of obtained hydroxy acryl acid resin The special numerical value of (%) and resin is shown in Table 3 below.
[table 3]
Table 3
The manufacture of hydroxyl polycarbonate polyester resin (L3)
Production Example 51
UM-90 (trade name, space are added in the reaction unit for possessing thermometer, thermostat, mixer and heating unit Bu Xingchan companies manufacture, makrolon ester) 270 parts, 136.8 parts of 6-caprolactone, appropriate Dibutyltin oxide (obtained hydroxyl The number-average molecular weight of polycarbonate polyester resin is 1700 or so amount), it stirs while being warming up to 170 DEG C.At 170 DEG C The reaction was continued, confirms that heating remains in more than 98.5%, is cooled down, discharged, obtain hydroxyl polycarbonate polyester resin (L3-1) solution.The number-average molecular weight of obtained hydroxyl polycarbonate polyester resin (L3-1) is 1650.
Production Example 52
UM-90 (trade name, space are added in the reaction unit for possessing thermometer, thermostat, mixer and heating unit Bu Xingchan companies manufacture, makrolon ester) 270 parts, 136.8 parts of 6-caprolactone, appropriate Dibutyltin oxide (obtained hydroxyl The number-average molecular weight of polycarbonate polyester resin is 2200 or so amount), it stirs while being warming up to 170 DEG C.At 170 DEG C The reaction was continued, confirms that heating remains in more than 98.5%, is cooled down, discharged, obtain hydroxyl polycarbonate polyester resin (L3-2) solution.The number-average molecular weight of obtained hydroxyl polycarbonate polyester resin (L3-2) is 2200.
Production Example 53
UM-90 (trade name, space are added in the reaction unit for possessing thermometer, thermostat, mixer and heating unit Bu Xingchan companies manufacture, makrolon ester) 270 parts, 136.8 parts of 6-caprolactone, appropriate Dibutyltin oxide (obtained hydroxyl The number-average molecular weight of polycarbonate polyester resin is 3000 or so amount), it stirs while being warming up to 170 DEG C.At 170 DEG C The reaction was continued, confirms that heating remains in more than 98.5%, is cooled down, discharged, obtain hydroxyl polycarbonate polyester resin (L3-3) solution.The number-average molecular weight of obtained hydroxyl polycarbonate polyester resin (L3-3) is 2900.
The making of clear dope (Z)
Production Example 54~79
Using the raw material described in table 5, to be stirred shown in aftermentioned table 5 with the use of vane-type stirring machine and Mixing.Then, butyl acetate is added in the mixture, and the viscosity of 25 seconds at 20 DEG C is adjusted to using Ford cup #No.4, is obtained To each clear dope (Z-1)~(Z-14).In addition, the cooperation of the clear dope (Z) shown in table 5 is the solid constituent matter of each ingredient Amount ratio.
Hydroxyl group containing polyester resin (L1-1) and hydroxyl polycarbonate resin (L2-1) in table 5 have following meanings.
Hydroxyl group containing polyester resin (L1-1)：" Placcel 305 " trade name, the manufacture of Diacel chemical industrial companies.Number is flat Average molecular weight 550.
Hydroxyl polycarbonate resin (L2-1)：" UM-90 " trade name, the manufacture of Yu Buxingchan companies, diol component is 1, 4- cyclohexanedimethanols and 1,6- hexylene glycol, the poly- carbon of quality=1/1 of quality/1,6- hexylene glycol of 1,4-CHDM Acid esters glycol.Number average molecular weight 900.
Described in organo-metallic catalyst (M) table that Details as Follows states 4 in table 5.
[table 4]
Table 4
The chemical industry companies' manufacture of * 1 Nikka Octhix Zinc Japan, Zn content 8%
* 2 zinc naphthenate Tokyo chemical conversion industry companies manufacture, Zn content 10.1%
* 3 zinc acetylacetonate Showa chemical companies manufacture, Zn content 25%
* 4 dibenzoic acid zinc and the manufacture of Wako Pure Chemical Industries company, Zn content 21.3%
* 5 zinc laurates and the manufacture of Wako Pure Chemical Industries company, Zn content 14.1%
The chemical industry companies' manufacture of * 6 Nikka Octhix Tin Japan, Theil indices 28%
* 7 K-KAT348King Industries companies manufacture, bi content 25%
* 8 DBU diazabicyclo endecatylenes
Polyisocyanate compounds (PI) in table 5 have following meanings.
Polyisocyanate compounds (PI)：" Sumidule N3300 " trade name firmly changes Bayer Urethane company systems It makes, the isocyanuric acid ester body of hexamethylene diisocyanate, solid constituent 100%, isocyanate group containing ratio 21.8%
[table 5]
Table 5
5 (Continued) of table
I-1. the making of coated plate is tested
As metal parts, the electro-deposition painting on the processed cold-rolled steel sheet of trbasic zinc phosphate (450mm × 300mm × 0.8mm) Fill heat-curable epoxy resin cationoid electrodeposition coating composition (trade name " ELECRON GT-10 ", Northwest paint company Manufacture) so that film thickness is 20 μm, being heated 30 minutes at 170 DEG C makes its curing.
As plastic components, prepare " TSOP-1 (TC-6) " (trade name, Japanese Polygem companies manufacture, 350mm × 10mm×2mm)。
Then, ungrease treatment is carried out with the surface of the gauze wiping metal parts containing petroleum benzin and plastic components.It will As above steel plate and polypropylene board the adjoining configuration obtained, as breadboard.
1st pigmented finiss (X-1)~(X-23) of the above-mentioned making of spray-coating on above-mentioned breadboard is so that dry film thickness For 10 μm, after standing 6 minutes at room temperature, " WBC-713T#1F7 " (trade name, the pass of electrostatic spraying as coloring base coating Western paint company manufacture, acrylic melamine resinae aqueous overcoating base coating coating, silver color is tinted, in table 6,7 It is denoted as " (Y-1) ") so that dry film thickness is 15 μm.Then, clear dope (Z-1)~(Z-26) of the above-mentioned making of electrostatic spraying makes It is 30 μm to obtain dry film thickness, places at room temperature after five minutes, is heated 30 minutes in 95 DEG C of baking oven, obtain being formed with multilayer The experiment coated plate of film.Various film performances as described below, which are carried out, using the multilayer film tests (table 6,7).
I-2. film performance is tested
Retouching property：Retouching property is evaluated by following flatness and distinctiveness.
Flatness：Use the W1 values measured by " Wave Scan DOI " (trade name, the manufacture of BYK Gardner companies) It is evaluated.The flatness in the smaller expression painting face of W1 values is higher.
S：W1 values are less than 10.0 value
A：W1 values are 10.0~20.0 values
C：W1 values are the values more than 20.0.
Distinctiveness：Use the W4 values measured by " Wave Scan DOI " (trade name, the manufacture of BYK Gardner companies) It is evaluated.The distinctiveness in the smaller expression painting face of W4 values is higher.
S：W4 values are less than 10.0 value
A：W4 values are 10.0~20.0 values
C：W4 values are the values more than 20.0.
Chipping resistance：In slungshot testing machine (the test piece holding station of trade name " Q-G-R gravels meter " (manufacture of QPanel companies) It is upper that experiment coated plate is set, by the compressed air of 480kPa~520kPa from the place of distance test (DT) coated plate 30cm at -20 DEG C The granite stones of granularity 6 and 100g experiment coated plate collisions are made with 90 degree of angle.Then, the experiment coated plate water that will be obtained It washes, dry, applying face adhesive fabric adhesive tape (manufacture of Nichiban Co., Ltd.).Then, above-mentioned adhesive tape is removed, with electro-deposition It is evaluated based on the area (referred to as peels off area) that the component of face and substrate exposes.
S：The ratio that the peels off area of plate suqare is applied compared with experiment is less than 5%
A：The ratio that the peels off area of plate suqare is applied compared with experiment is more than 5% and less than 10%
C：The ratio of the peels off area of plate suqare is applied compared with experiment more than 10%.
Water-fast adhesion：Will experiment coated plate impregnate in 40 DEG C of warm water 240 it is small when, pull out, dried at 20 DEG C 12 small The multilayer film for testing coated plate in a manner of reaching bottom is cut into clathrate with knife, makes size 2mm × 2mm's by Shi Hou Gridiron pattern 100.Then, the adhesive tape of fitting bonding in its surface, chess is investigated after quickly removing adhesive tape at 20 DEG C The Restzustand of disk lattice film, according to following benchmark evaluation water resistances.
S：Gridiron pattern film remains 100, and the smaller crimping of film is not generated in the edge of knife cutting
A：Gridiron pattern film remains 100, and the smaller crimping of film is generated in the edge of knife cutting
B：Gridiron pattern film remains 90~99
C：The residual number of gridiron pattern film is below 89.
Ethanol petrol resistant：It is illustrated according to component.
The situation of plastic components：By each experiment coated plate in the experimental liquid of the weight ratio of gasoline/methanol=90/10 at 20 DEG C Dipping, expansion, the painting surface state of peeling when observation was by 30 minutes, is evaluated under following benchmark.
S：Completely no exception,
A：Expansion, peeling less than 3mm,
B：The expansion of 3mm~below 5mm, peeling,
C：Expansion, peeling more than 5mm.
The situation of metal parts：By each experiment coated plate in the experimental liquid of the weight ratio of gasoline/methanol=90/10 at 40 DEG C Dipping, expansion, the painting surface state of peeling when observation was by 60 minutes, by being commented with the same benchmark of the situation of plastics Valency.
Weatherability：Foundation JISK 5600-7-7 uses " super xenon test apparatus " (Xu He testing machines company manufactures, Weathering tester) it moistens and cycles in test film：18 minutes/2 it is small when, black flour plate temperature：To applying under conditions of 61 DEG C~65 DEG C Each experiment coated plate loaded on metal parts carries out promotion atmospheric exposure test.Then, reach 1 in the irradiation time of lamp, 000 it is small when, 2,000 is small and the multilayer film of breadboard is cut into grid in a manner of reaching bottom with knife at the time of when 3,000 is small Shape makes the gridiron pattern 100 of size 2mm × 2mm.Then, the adhesive tape of fitting bonding in its surface, it is quick at 20 DEG C Remove the Restzustand that gridiron pattern film is investigated after the adhesive tape.
S：Gridiron pattern film remains 100, and the smaller crimping of film is not generated in the edge of knife cutting
A：Gridiron pattern film remains 100, and the smaller crimping of film is generated in the edge of knife cutting
C：The residual number of gridiron pattern film is less than 99.
Pot life (storage period)：Using Ford cup #No.4 measure each clear dope 6 it is small when after 20 DEG C at it is viscous Degree.The pot life after coating composition and evaluation are made by following reference measurement.
S：Less than 35 seconds
A：36 seconds~40 seconds
C：Gelation
-：It is unmeasured
[table 6]
Table 6
6 (Continued) of table
6 (Continued) of table
[table 7]
Table 7
II-1. the making of coated plate is tested
As metal parts, the electro-deposition painting on the processed cold-rolled steel sheet of trbasic zinc phosphate (450mm × 300mm × 0.8mm) Fill heat-curable epoxy resin cationoid electrodeposition coating composition (trade name " ELECRON GT-10 ", Northwest paint company Manufacture) so that film thickness is 20 μm, being heated 30 minutes at 170 DEG C makes its curing.
As plastic components, prepare " TSOP-1 (TC-6) " (trade name, Japanese Polygem companies manufacture, 350mm × 10mm×2mm)。
Then, ungrease treatment is carried out with the surface of the gauze wiping metal parts containing petroleum benzin and plastic components.It will As above steel plate and polypropylene board the adjoining configuration obtained, as breadboard.
1st pigmented finiss (X-1) of the above-mentioned making of spray-coating on above-mentioned breadboard so that dry film thickness is 10 μm, After shaping 6 minutes at room temperature, electrostatic spraying so that dry film thickness is 15 μ as the 2nd pigmented finiss (Y-1) of coloring base coating m.Then, the clear dope (Z-15), (Z-17), (Z-19), (Z-24), (Z-25) or (Z-26) of the above-mentioned making of electrostatic spraying makes It is 30 μm to obtain dry film thickness, places at room temperature after five minutes, is heated 30 minutes in 75 DEG C of baking oven, obtain being formed with multilayer The experiment coated plate of film.Various film performances as described below, which are carried out, using the multilayer film tests (table 8).
II-2. film performance is tested
Carry out similarly operation, same evaluation described in the project with above-mentioned " experiment of I-2. film performances ".
[table 8]
Table 8

Claims (7)

1. a kind of method of forming layered coating film, the method is to carry out the method for forming layered coating film of following process successively：
(1) on the coated article containing metal material and plastic material aqueous 1st pigmented finiss (X) of application and formed uncured The process of 1st coloring film；
(2) obtained by process (1) it is uncured 1st coloring film on aqueous 2nd pigmented finiss (Y) of application and formed not The process of cured 2nd coloring film；
(3) transparent paint coating (Z) is uncured to be formed on the uncured 2nd coloring film obtained by process (2) The process of transparent coating；And
(4) by formed in process (1)~(3) it is uncured 1st coloring film, it is uncured 2nd coloring film with And uncured transparent coating is heated so that this 3 films while cured process, which is characterized in that
Polyolefin-based resins (A), the acid value of aqueous 1st pigmented finiss (X) containing chlorine-free be 1mgKOH/g~ The waterborne polyurethane resin that 30mgKOH/g and the time at a temperature of 20 DEG C until film forming are 5 minutes~20 minutes (B), there is the blocked polyisocyanate compound (C) of nonionic hydrophilic radical and conductive pigment (D),
Aqueous 1st pigmented finiss (X) described in application and make its cure obtained from thickness be 5 μm of cured coating film in wavelength Average transmittance at 360nm~420nm is less than 1%；
Wherein, the blocked polyisocyanate compound (C) with nonionic hydrophilic radical is with selected from the following general formula (I) shown in the blocked isocyanate base shown in blocked isocyanate base, the following general formula (II) and the following general formula (III) shown in At least one of blocked isocyanate base blocked isocyanate base blocked polyisocyanate compound,
[chemical formula 1]
In formula (I), R1、R2、R4And R5Independently represent the alkyl of carbon number 1~12, R3Represent the straight chain of carbon number 1~12 The alkylidene of shape or branched,
[chemical formula 2]
In formula (II), R2、R3、R4And R5With above-mentioned R2、R3、R4And R5It is identical,
[chemical formula 3]
In formula (III), R2, R3, R4 and R5 are identical with above-mentioned R2, R3, R4 and R5, and R6 represents the alkyl of carbon number 1~12.
2. method of forming layered coating film according to claim 1, wherein, the clear dope (Z) is contained
Hydroxyl value be 140mgKOH/g~210mgKOH/g, weight average molecular weight be 5000~18000 and glass transition temperature be- The acrylic resin (K) of 25 DEG C~20 DEG C of hydroxyl.
3. method of forming layered coating film according to claim 2, wherein, the clear dope (Z) is contained
It is that the polyester resin (L1) of 500~2500 hydroxyl, number-average molecular weight are 500~2500 to contain selected from number-average molecular weight The polycarbonate resin (L2) and number-average molecular weight of hydroxyl are the polycarbonate polyester resins (L3) of 500~2500 hydroxyl In at least one kind of resin.
4. method of forming layered coating film according to claim 1, wherein, the clear dope (Z)
On the basis of the resin solid content quality total amount of clear dope, containing 30 mass %~70 mass % hydroxyl third Olefin(e) acid resin (K)；
Compared with the solid constituent total amount of the acrylic resin (K) of hydroxyl, containing below 100 mass % selected from hydroxyl In the polycarbonate polyester resin (L3) of polyester resin (L1), the polycarbonate resin (L2) of hydroxyl and hydroxyl at least 1 kind of resin；And
Compared with the solid constituent total amount of the acrylic resin (K) of hydroxyl, the polyisocyanate esterification containing below 200 mass % Close object (PI).
5. method of forming layered coating film according to claim 3, which is characterized in that above-mentioned clear dope (Z) is also contained
The organo-metallic catalyst (M) that is made of zinc compound and amidine compound, polyisocyanate compounds (PI) and
Selected from beta-diketon class, beta-keto acid esters, malonic acid esters, the β ketones with hydroxyl, the β aldehydes with hydroxyl with And the β at least one kind of end-capping reagents (N) having in the esters of hydroxyl,
The amount of the organo-metallic catalyst (M) compared with hydroxyl acrylic resin (K) ingredient, the polyester selected from hydroxyl In polycarbonate polyester resin (L3) ingredient of resin (L1) ingredient, polycarbonate resin (L2) ingredient of hydroxyl and hydroxyl The total amount of at least one kind of and polyisocyanate compounds (PI) ingredient be the mass % of 0.05 mass %~5.
6. method of forming layered coating film according to claim 5, which is characterized in that the amount of the end-capping reagent (N) compared with Acrylic resin (K) ingredient of hydroxyl, polyester resin (L1) ingredient, the polycarbonate resin of hydroxyl selected from hydroxyl (L2) at least one kind of and polyisocyanate compounds (PI) in polycarbonate polyester resin (L3) ingredient of ingredient and hydroxyl The solid constituent total amount of ingredient is the mass % of 0.7 mass %~25.
7. according to method of forming layered coating film according to any one of claims 1 to 6, wherein, it is described containing metal material and The coated article of plastic material is to assemble the coated article that metal material and plastic material form.
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