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GB2510271A - Copolymer, aqueous coating composition containing copolymer, and method for forming multilayer coating film - Google Patents

Copolymer, aqueous coating composition containing copolymer, and method for forming multilayer coating film Download PDF

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Publication number
GB2510271A
GB2510271A GB1404956.3A GB201404956A GB2510271A GB 2510271 A GB2510271 A GB 2510271A GB 201404956 A GB201404956 A GB 201404956A GB 2510271 A GB2510271 A GB 2510271A
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monomer
polymerizable unsaturated
unsaturated monomer
mass
component
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GB2510271B (en
GB201404956D0 (en
Inventor
Takeshi Fujii
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Kansai Paint Co Ltd
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Kansai Paint Co Ltd
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Priority claimed from GB201205822A external-priority patent/GB2487020B/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • 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
    • C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
    • C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
    • C08G18/0861—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers
    • C08G18/0866—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers the dispersing or dispersed phase being an aqueous medium
    • 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
    • C08G18/62—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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/81—Unsaturated isocyanates or isothiocyanates
    • C08G18/8108—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group
    • C08G18/8116—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group esters of acrylic or alkylacrylic acid having only one isocyanate or isothiocyanate group
    • 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
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/06—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/29—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for multicolour effects
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/36—Pearl essence, e.g. coatings containing platelet-like pigments for pearl lustre
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/38—Paints containing free metal not provided for above in groups C09D5/00 - C09D5/36
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
    • C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
    • C09D5/443—Polyepoxides
    • C09D5/4457—Polyepoxides containing special additives, e.g. pigments, polymeric particles
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/43—Thickening agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/52—Two layers
    • B05D7/53—Base coat plus clear coat type
    • B05D7/532—Base coat plus clear coat type the two layers being cured or baked together, i.e. wet on wet
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/062—Copolymers with monomers not covered by C08L33/06
    • C08L33/064—Copolymers with monomers not covered by C08L33/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/062—Copolymers with monomers not covered by C08L33/06
    • C08L33/066—Copolymers with monomers not covered by C08L33/06 containing -OH groups
    • C—CHEMISTRY; METALLURGY
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

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Abstract

A copolymer comprising copolymerization of a monomer component mixture (m) that includes: (m-1) a macromonomer having (i) a backbone that comprises a polymer chain having a number average molecular weight of 1,000 to 10,000 and polymerising a monomer component (I) that contains 5-100 mass% of a C4-C24 alkyl-containing polymerisable unsaturated monomer (a), and (ii) a polymerisable unsaturated group; and (m-2) a polymerisable unsaturated monomer containing a hydrophilic group; wherein the copolymer is a graft polymer having a main chain and a side chain, component (m-2) contains at least one kind of hydrophilic group selected from acrylic acid and methacrylic acid, and wherein content of component (m-1) is 1-40 mass%, and component (m-2) is 5-75 mass% based on the total of monomer component (m). Component (m-2) can optionally be a non-ionic polymerisable unsaturated monomer containing at least one kind of hydrophilic group selected from N-substituted (meth)acrylamide having a polyoxyalkylene chain, and N-vinyl-2-pyrrolidone, and wherein content of component (m-1) is 1-29 mass%, and content of component (m-2) is 20-99 mass% based on the total of monomer component (m). The proviso is that a graft copolymer consisting of (A) a main chain containing an N-substituted (meth) acrylamide in a monomer component and having a lower critical solution temperature in water of 40oC or higher; and (B) a hydrophobic side chain is excluded. Also disclosed is an aqueous coating composition containing the copolymer and a method for forming a multilayer coating film containing the copolymer.

Description

DESCRIPTION
TITLE OF INVENTION: COPOLIMER, AQUEOUS COMING CoMPosI'rIoN COTKINING COPOLYNER, AND METHOD FOR FORMING MULTILAYER COATING
S FILM
TECHNICAL FIELD
The present invention relates to copolymers, and viscosity'-controiling agents including the seine, Specifically, the invention relates to additives for coating compositions, particularly to copolymeis suitable as viscosity-contro±lrng agents that can develop viscosity -in aqueous coating compositions that contain surfactant s. The invention aLso relates to aqueous coating compositions that contain such 15, conolymers, and methods for forming multilayercoatina films using such aqueous coating compositions.
CROSS-REFERENCE TO RELATED APPLICATIONS
Th..i.s appl.i.ca ion claims priority -to JPApplication No. 2009-249204, filed october 29, 2009, JP Application No. 2010- 30442, filed February 15, 2010, and JP Application No. 2010-- 79177, filed March30, 2010, the disclosure of which is incorporated herein by reference in its entirety.
BACKGROUND AIC
Objects' (substrates) to be coated that require high levels of appearance, such as automobiles, are generally painted using methods that employ atomization of coatin compositions, i.n consideration of, for example, the appearance of the coating film formed, and production efficiency. Spray painting and rotational atomizing painting are specific examples of-such painting methods.
Generally, the coating corvposition used for atomization partnq ioud nrelerabi 1 a e iuw v.scos v, aru forn snal granules when released in a spray or when atomized as in, for example, rL,t.at1on. I. atomization, in order to produce a coatinQ film with excellent smoothness, Once apul ted to the substrate to be coateCi, toe coating composcion should prer.erably have nigh viscosity, which discourages mixing with the overlaid coatinci S composition and produces a r oating film with excellent distinctness of image (hereinafter referred to as DOi) When the coating composition con:ams a luster pigment such as an aluminium pigment, the high coating composition viscosity after the compos ton has been applied to the substrate rest..ict the movement of the luster piment in the coating composition, and thus produces a coating film that has good lust.ar: Generally. a coating film with good luster is one in which brightness changes over a wide range depending on the viewing angle of the coating film, and in which the luster pigment in the coating film is 15. relatively uniform, thus producing hardly any metallic mottling.
Coating fi.lxos that exhibit such large brightness chances rjepending on the viewing angle are generally described as having a high flip-flop property.
For these reasons, in terms of forming a coating film having superior appearance, it is preferable that the coating composition have low viscosity under high rate of shear as in at:omizi.ng, and high viscosity under low rate o.f shear altec the.
application. In other words, it is preferable LhaL Lhe coating composition be one in which the viscosity decreases with an increase in rate of shear.
Such a coating composition that lowers its viscosity while increasing rate of shear can he produced using, :1st example, a method in which an associated thickener is blended into the coating composition. The associated thickener is generally a thickener that includes a hydrophilic portion and a hydrophohi.c portion per molecule, and that effectively exhibits a thickeninc effect with the network structure formed in an aqueous medium by the adsorption of the hydrophobic portion onto the surfaces of the pigments or emulsion granules in the coating composition, or by the association of the hydrohobic portions.
The associated thickener generally develops viscosity with the network structure formed by hydrophobic _ interaction, Associative strength:is relatively weak in hydrophobic interaction, and as such the network structure is disrupted and the viscosity decreases upon applying a large shear force.
Specif:caily, the coating composition containing the m-'sociated thickener has the: characteristic of lowering its viscosity with an increase in rate of shear.
Recent concerns over envi.rorentai. pollution caused by the vaporization of organic solvents have led to the development of aqueous coating compositions.
Aqueous coating compositions may typically include a surfactant used to disperse a hydrophobic resin component in water.
However, the use of the associated thickener in such aqueous coating compositrons containing a surfactant is problematic, because the viscosity-developing effect of the associated thickener may become weak, and 001 or luster of the resulting coating film may he lowered. Specifically, because the aqueous coating composition has low viscosity upon being applied to the substrate to be coated, the coating composition may mix with the overlaid coating composition and lower 001 of the resiiting coating film; or the luster pigments, when contained in the aqueous coating composition, may move in the coating composition upon application and disorient themselves, lowering the flip-flop property or causIng metallic mottling. Attempts to increase the viscosity upon application by increasing the content of the associated thickener in the aqueous coating composition often result in a coating film with poor smoothness, because the increased thickener content also increases the viscosity under high rate of shear, and increases the size of the coating composition qranules produced when atomizing the coatrng composition.
For example. Patent Literature I describes a viscosity.--con..t rolling agent that. includes a hydrophobic portion and a --4 hydrophilic portion, obtained by hydrophobic modification of a hydrophiLtc polymer, and/or hydrophilic modification of a hyaropnobic polymer. The viscosity-controlling agent is described as being capable of reducing the concentration.
dependence of the aqueous dispersion viscosity. Further.
accorcu.ng to this pubiscatron, an aqueous coating composition that uses the v.iscosi.ty--contro.ii.inq agent can exhibit stable flowability, and can stably produce a coating. film with a good finish, regardless of the paint conditions, partacuiarly the temperature and humidity conditions. However, viscosity development by the v.iscosity-controi.ling agent is not always sufficient. 3pecifia1ly, sufficient viscosity may not be obtained when the viscosity--cort ml ing agent is used in a coating composition tb-at contains a surfactant. In this case, the resull:ing coating film may suffer from poor DOT and poor fli.-tlop property, or may produce metallic mottling.
Patent Literature 2 describes an associated thickener prodaced by adding one molecule of alkenyl succinic anhvdride or al.kyl succinic anhydride to a polyethylene glycol compound for each of at least two am. mo groups attached to the ends of the poyethy1ene ylyco.. comnound molecule. The associated thickener is described as being nesarahi.e as a thickener for..a texes and aqu eons coating compositions for its ability to improve the ease of solution adjustment without accompanying large viscosity changes following changes in the amount of associated thickener used, and to make quality control of the products easier.
However, viscosity deveiopment oy tne assoc:t.ated thicKener.15 hut always sufficient -Specifically, sufficient viscosity may not be obtained when the associated thickener is use.d in a coating composition that contains a surfactant. In this case, the resulting coating film ma: suffer from poor DOl and poor flip-flop property, or may produce metallic mottling.
Patent Literature 3 describes an aqueous coating composition that includes an emulsion resin (A) of a specific structure, a speci.fi.c vi.scositycontro.l.ling agent (B), and a 5-..
hydrophobic solvent (C) The aqueous coating composition described as being capable of. forming a coating film that has reduced metallic motti. mc, and excel lent f1ipf1op property and smoothness. However, a coating film with suff.i cient 001 and luster, or a coating film with sufficient water resistance cannot always he obtained even with the use of this aqueous coating composition.
CITATION LIST
Patent Literature PTL 1: Japanese tJnexami.ned Patent Publication No. 2300-4662 PTL 2: Japanese Unexamined Patent Publication No. 1997-272796 PTL 3: Pamphlet of W02307/126134 SUMM7RY OF INVENTION Technical. Problem it is an object of the present invention to provide a 23 copolmer having the characteristic of easily developing viscosity, and lowering its viscosity with an increase in rate of she-ar, particularly a;plner having the cha.racteristi.c of deveiopinq viscosity, and lowering its viscosity with an increase. in rate t shear, even in an aqueous coating conosition that contains a surfactant. Another object of the present invention is to provide a coating composition that contains the copolymer, and with which a coating film having superior 001 can be formed. It is another object of the inventibn to provide a coating composition that includes the copoI.yner and a luster pigment, and with which a coating film having superior luster with a high flipflop property and suppressed metallic mottling can be formed. Yet anothet object of the invention is to provide a coating filmform.i.nq method that uses the coating ccmposition and an article painted with the coating cot posi tton.
Solution to Problem The present inventors conducted intensive studies to achieve the foregoing objects, and found that a. copolymer of a graft polymer structure containing a main chain as obtainable by polymerizing a monomer component that includes a polymerizable unsaturated monomer containing a hydroh.i1i.c group, and a side chain as a relatively high molecuiar weight polymer obtainable by polymerizing a monomer component that contains a specific oolymerizable i.nsaturated monomer has the characteristic of easii.y developing viscosity, and lowering its viscosity with. ar.
increase in rate of sheen Specifically, the copolymer has the characteristic of develoolna viscosity, and lowering, its viscosttvwth an increase in rat.e or sneer even In an aqueous coating composition that contains a surfactant.
Specifical]y, the present invention provides a copolymer, a viscosiLycontrolling agent including the same, an aqueous coating composition containing the copolymer, a coating fii.mfor'sdng method that uses the aqueous coating composition, and an article painted with the aqueous coating composition.
Item 1, A copolymer obtainable by copolymerization of a monomer component (xii) compn sing: (tm--I) a macrornonomer having (iJ a backbone that comprises a polymer chain having a tiumeer average molecular weight of.: -tOOO to 10,000 obtainable by polyme.ni.zing a monomer coronent (I) that contaIns' 5 to 100 mass% of a 04-C24" aikyl-containing poiy.merizable unsaturated monomer (a), arid (ii) a polymerirable unsaturated group; and cm-2) a polvinerizabie unsaturated monomer containing a hydroph i. I ic group.
Item 2. The copolymer: according to Item 1, wherein component ui OflI OLIC potynet a L'lc UE -i i. ra I n i.mor co ta ni ig at at u' nc ot' nuzc ri iu arop selcced Iron the qr-up cotisisti.ng of Nsubstituted (moth) acrylamide, polymerimhle unsaturated monomer having a poI.oxyalkyi.ene chain, and N--vinyl- 2--vrro.l.id.one, and wherein the content of component (rn--i) is in a range of from 1 to 29 mass%, and the contertof component (m-2) is in a range of from 20 to 99 mass%, based on the total mass of irtonomer comoonenL (m)
S
Item 3. The copo.iymer according to Item I or 2, wherein monomer component (I) contains, at least a part thereof, 5 to 60 mass% of a hydroxy-containino polymerizable unsaturated monomer, based on the total mass of monomer component (I item 4. The copolymer according to any one of items 1 or 3, wherein component (m-2) is a polymerizable unsaturated monomer containing at least one kind of hydrophi l.ic group selected from the group consistifF; of acrylic acid and methacrylic acid, and wherein the content of component (rn-i) is-S-in a range of from 1.
to 40 mass%, and the content of component (m-2) is in a range of f:rom 5 to 75 mass%, based on the total mass of monomer component (in) item 5. M aqueous coating composition containing the copolymer according to any one of ifems I to 4 and a film-forming resin (A) I-tern 6. The aqueous coating composition according-to Item 5, wherein the film-forming resin (A) is a water-dispersible 25-hydroxy-containing acrylic resin (Al') having an acid value of I to 100 mg KOfi/g and a hydroxy value of 2. to 100 rag KOH/g, obtainable through copolymerization of monomer component (h) comprising Sto 70 rnass% of a hydroehobic o1ymerizable unsaturated monomer (b-i) , 0,1 to 25 mass% of a hydroxy-containing polwnerizahle unsaturated monomer (b-2), Ofl to 20 mass% of a carboxy-containing polymae.rizable unsaturated monomer (b--3) , and Oto 94-3 mass% of a polymerizabie unsaturated monomer (h-4) other than the poi.vmenr.zabe unsaturated monomers (b--li to (b-3) -Item 7. The acueous coating composition according to Item 5 or 6, wherein component rn---2) is at least one kind of polymerizabie unsaturated monomer selected from the group consisting of N--substituted (moth) acrylasnide, polymeri zabl.e unsaturated monomer: having a polyoxyalkylene chain Nvinyl-2--vyrrolidone, 2-hydroxyethyl acry.l.ate, acrylic acid and methacrylic acid.
Item 8. The aqueous coating composition according to any one of-items 5 to 7, wherein monomer component ün) contains 1 to 40 rnass of component; (rn-I) and 5 to 99 mass% or. component (u--2) based on the total mass c-f monomer component (in) Item 9. The aqueous coat.tnq oomposit.wn according to arty one of Items 6 to B, wherein the water--dispersible hydroxy-containing acrylic resin (Al') is a core-shell-type water---isper:s.h.i.e hydroxy-containing acrylic resi.n (A].' -1) which has a core-shell structure having, as a core, cnpoiymer (I) containing. as monomer components, (L]. to 30 rmess1f-, of a poi.ymei..izable unsaturated monomer having two or more polymerizahie unsaturated groups per molecule and 70 to 99.9 mass% of -a oiymerizable unsaturated monomer having one polwnenizabl.e unsaturated group per molecule, based on the total mass of monomer components constituting the core, arid wherein the core-shell-type water--dispersible hydroxy-containing acrylic resin (A1'-l) contains 5 to 70 mass% of a hydrophobic polymerizable unsaturated mononiez (b-i), 01 to 25 mass% of a hydroxy-containing polwerizahie unsaturated monomer (h-2), 0l to 20 mass% of carboxy-containing polymerizabie unsaturated monomer (b-3) , arid 0 to 94.8 mass% of a polymerizable unsaturated monomer (b-4) other than the polymerizable unsaturated monomers (b-i) to (h-3), based on the total mass of monomer components constituting the core and the shell. -Item 10. The aqueous coat.ng composition according to any one of items 6 to 3, wherein the water-dIspersible hydroxy--containing.
acrylic resin (Al.') is a core-shei.l-type water-dispersi.hie hydroxv---contairiing acrylic resin (Al' -2' comorising a core portion that is ci copolymer 1) consksting or, as monomer components, about 0.1. to 30 mass% of a polymer.izable unsaturated monomer having two or more poi.ymerizable unsaturated qrouos per rnoi.ecul.e and about 70 to 99.9 mass% of a polymerizabie unsaturated monomer having one poi.ymerizahle unsaturated group per molecule; and a sheLl portion that is a copo.iymer (Ii) consisting of, as monomer components, S to 80 mass% of a hydrophobic polymerirable unsaturated monomer (b-I) 0.1 to 50 mass% of a hydroxy--contai.ning pol.yrm..r izable unsaturated monomer (b-2), 0.1 to 50 rnass% of a carboxy-containing polymerizable unsaturated monomer: (b-3), and 0 to 94.3 mas% of polym.eri.zable unsaturated monomer (h-4) other than the polymerizable unsaturated monomers (b-i) to (h--3), and wherein the solids content mass ratio of copolymer (I) to copolymer (II) is in a range of 5/95 to 9515.
item 11.. Item The aqueous coating composition according to any one of items 5 to 10, wherein the film-forming resin (A) is a resin having art ester bond.
item 12. The acueous coating composition according to any one of items.5 to ii, wherein the film-forming resin (A) is a water-dispersible acrylic resin ohtai.nahi.e by emulsion polymerization using a suri:actant Item 13. An article coated with the aqueous coating composition accordincz to any one of Inems 5 to 12 Item 14. A mthod for forming a multilayer coating film, comprising the steps of: (1) applying the ac:jueous coating composition according to any one of Items S to 12 to an object to form a base coating film; -l0 2) applying a ci ear coat. lug conxposit.on on an uncu.red base coating film to form a clear coating film; arid (3) heating the uncured base coating film and uncured clear coating film to simultaneously cure both coating films.
Item 15. A method for formine a multilayer coating film, comprisiri the steps of: (1) applying a first coloring coating composition to an object to form a first colored coating film; (2.) applying the aqueous coating conposition according to any one of Items 5 to 12 on the uncured first colored coating film to form a second colored coating film; (3) applying a clear coating composition on the uncured second colored coating film to form a clear coating film; and (4) simultaneously heat-curing the uncured first colored coating film, uncured second colored coating fi.J.m and uñcured clear coating flint item 16. An article having a multilayer coating film formed by 2(3 the method according to item 14 or 1.5.
Item 17 vi.scosi.ty--controlling agent comprising the copoiyer accordxng to any one of Items; I to 4
ADVANTAGEOUS EFFECTS OF INVENTION
A copolymer of the present invention has the characteristic of easily developing viscosity, and lowering its-viscosity with an increase:i.n rate of shear. Specifically, the copolymer has the characteristic of developing viscosity, and lowering its viscosity with an increase in rate of shear even in an aqueous coating composition that contains a surfactant. An aqueous coating composition of the present invention can he used to fo.un a coating film having superior 001. Further, an aquecus coating composition of the present invention can he used to form a coating film that has high flip--flop property, and superior luster with suppressed metallic mottling.
DESCRIPTION OF EMBODIMENTS
r copo.lymer of the present invention is described below in detail.
I. c.opoJ...iner at the Present Invention A copolymer of the present invention can he obtained by copciymerlzation of a monomer component (in) that includes: (n--i) a macromonomer having (i) a backbone that comprises a polymer chair! having a nuniber average molecular weight of 1,000 to 10,000 obtainable, by po.lymerizing a monomer component (I) that contains 5 to 100 mass% of a C4-C24 alkyl-containing polymerizable unsaturated monomer (a) * and (ii.) a polymer i.zahle unsaturated group; and (m-2) a poi.ymerizahle unsaturated monomer containing a hydrophilic group.
A copolymer of the present Invention has the characteristic of easily de7elop.ing viscosaty, and lowering its viscosity with an increase in rate of shear. Specifically, the copolymer has the characteristic of develoning viscosity, and lowering its viscosity wit.Ii an increase in rate or shear even in an aqueous coating composition that contains a surfactant, With such a superior viscosity characteristic, a copolysner of the present invention is preferably used as a viscosi.ty-controLl.ing agent Further, because of the ability to form a coating film having excellent 001 and luster, a copolymer of the present invention is particularly suitable as a viscosity-controllinq agent for coating compositions.
:30 C4-C24 Alkv'lContaininm Pclvmerizahl.e Unsaturated Monomer:;a For examle, monoesterified products of (meth) acrylic acid with a monohydric alcohol having a C4-C24 aikyl group can be used as the 04-024 aikyi-contaunng o1ymenzabie unsaturatec monomer (a) Specific examples include alkyl or cycloalkyl (meth) acrylates such as n-hutyl (meth) acrylate, isobutyl (meth)acrylate, tert-butyl (math) acrylate, pentyl (meth)acrylate, hexyl Oneth) acrylate, octyl. (meth) acrylate, 2-ethyihe*yJ.
(meth) acrylate, nonyl (math) acryicte, dodecyl (math) acrylate, lauryl (meth)acrylate, tridecyl (math) acrylate, stearyl (math) acrylate, isostearyl (mth) acrylate, cyclohexyl (meth)acryi.ate, r.nethyl cycl.ohexyl. (math) acry.].ate, tert-butyl cyclohexyl (math) acrylate, cyciododecyl (math) acrylate, isohontyl. (math) acrylate, adamantyl (math) acry.i.ate, tricyclodecanyl (math) acrylate, etc. These may be. used singly, or in a cothbination of two or more.
The tern "(math) acr:yiate" used in thi.s specii.i.cation means acrylate or methacrylate, and the term " (math) acrylic acid" means acrylic acid or nethacrylic acid. Additionally, the term (math) acryloyl" means acryloyl or methacryloyl, and the 1.5 tent "(meth) acryiamide" means "acrylamide or methacryiamide".
In terms of 501 of the resulting coating film, the C4-C2.4 alkyi-conthining oolwnarizabie unsaturated monomer (a) is preferably a pol.uerizahl.e unsaturated monomer having at' 6-CiB alkyl group, more preferably a pol.ymarizahle unsaturated monomer having a CE-CIB alkyl group. 2-Ethylhexyl methacrylate, dodecyl metbacrylate, and tridecyl mathacrylate are preferable, and 2-ethyihexyl methacrylate is particularly preferable.
Monomer Component ç I The monomer component (I) contains 5 to 100 mass% of the C4--C24 alkyl--cont.aining poiymerizab.].e unsaturated. scnomer (a) In tens of DCI of the resulting coatinq film, it is preferable that the content of the C4-C24 a ikyl-containing polymerizable unsaturated monomer (a) in the monomer component (1) be 30 to 95 mass%, preferably 45 to 90 nass%, further preferably 55 to 85 mass%.
The monomer component (I) may also contain a polymerizable unsaturated monomer (b), in addition to the C4-C24 aikyl-containing polymerizable unsaturated monomer (a) In this case, the monomer component (1) includes the 0-4-024 al kyl-containing polymerizable unsaturated monomer (a) and a poi.ymer.izahle unsaturated monomer (b) that is difierent from the c4c24 alky1containing poi'menzabie unsaturated monomer (a) Examples of the poivinerizable unsat urated monomer (b S that is aitferent from the (4-C24 a.].KYF-conta.irrLng po.Lymeri.zabie unsaturated monomer (a) include: alkyl (meth) acrylates having a C1.C3 alkyl group, such as methyl (math) acrylate, ethyl.
(math) acrylate, n-propyl (math) acrylate, isceropyl meth) :scryi.ate, etc..; aromatic r..ng-containing poi.vmen.zabie unsaturated monomers such as benzyl (moth) acrylate, styrene, a methyl atyrene, vinyl t:oluene, etc.; po.lymerizabie unsaturated monomers having an alkorysilyl group, such as vinyj.trimethoxysiiane, vinyJ.triethoxysil.ane, vinyl tris (2-methoxvethoxy) silane, y (meth) acry].oyi.oxypropv.itrimethoxys.i lane, y--(math) acryloyloxypropyltriethoxysikme, etc..; perfiuoroalkyl (math) acrvlates such as perf.l.uo.rohutyiethyl (math) acryi.ate, perfiuorooctylethyl (math) acrylate, etc..; polymerizable unsaturated monomers having a fluorinated alkyl group, such as fi.uo.roolen.n, etc; polvmenzahle unsaturated monomers having a photopolymerizable functional group, such as a maleimide aroup, etc.; vinyl compounds such as N-vinyl-2-pyrrolidone, ethylene, butadiene, chi oropre.e, vinyl. propionate, vinyl acetate etc..; hydroxy-containing polymerizable unsaturated monomers such as monoesterified products of (moth) acrylic acid with a dihydri.c alcohol having 2 to 6 carbon atoms (e.g, 2-hydroxyethvl (math) acrylate, 2-hydroxypropyl (moth) acrylate, 3-hydroxypropyl (math) acrylate, and 4-hydroxybutyl (meth)acrylate), a-caprolactone modified products of the monoesterified products of (math) acrylic acid with a dihydric alcohol having 2 to 6 carbon atoms, N-hydroxvmethyl (math) acryiam:i.de, allyl alcohol, (math) acrylates havzng hydroxy--bernunaten poJ.yoxyetnylene chains/ etc..; carboxy-contalning olymerizable unsaturated monomers such as (math) acrylic acid, maleic acid, crotonic acid; 3-carboxyethyl acrvlate, etc.; pol;,merizable unsaturated monomers having at least two polymer.i.zahle unsaturated groups per clecule, sch as allyl(meth)acrylete, ethylene glycol di (meth) acrylate, triethylene clycol di (math) acrylate, tetraethyl.ene alycci di (math) acrylate, 1, 3-butylene qi.ycol.
di (meth) acryl.ate, trimethyloi.prcpane fri (met.h) acrylate, 1,4-butariediol di (meth) acrylate, neopentyl glycol di (math) ac:rylate, 1, 5--hexanedioi. di (meth) acrylate, pentaerythritol di (math) acrylate, pentaerythritol tetra (math) acrylate glycerol di (meth)acrylat.e, 1,1, 1-trishydroxymethy]et.hane di (math) acrylate, 1,1, i-trishydroxymethylethane tn (math) acrylate, 1, 1, 1- :1.0 tri.shydroxymethyipropane fri.. (meth) acrylate, trial lyl isocyanurate, diallyl tereplithalate, divinylberizene, etc.; n1trogen-conta1n.Lng polymerizahie unsaturated monomers such as (meth) acrylortitrfle, (math) acrylaraide, N, N-dimethylanünoethyl (math) acrylate, N, Wd.tethd.aminoethyl (math) acrylate, N,N-d:Lmethv1uLnopropyl (meth)acrylamide, an adduct of givcidyl (meth)acrylate with amine compounds, etc.; epoxy=containing polymenizable unsaturated monomers such as glycidyl Cneth)acrylate, ---methylglycidyl (meth)acrylate, 3,4-epoxvcyclohexyimethy.l (math) acrylate, 3, 4-epoxycyciohexylethyl (meth) acrylate, 3, 4-epoxycyclohexylpropyl (math) acrylate, ailyl glycidyl ether, etc.; isocyanato--containing poiymeriaable unsaturated monomers such as 2---isocyanatoethyl (meth) acrylate, m-'isopropenyi-a,a----dimethyl benzyi Isocyanate, etc.; (math) acrylates having alkoxy'-termlnated polyoxvethyl.ene chains; carbonyl-containing polymerizable unsaturated monomers such as acrolein, diacetone acrylamide, diacetone methacrylamide, acetoacetoxylethy.l methacrylate, forinyl styrol, vinyl alkyl ketone having 4 to 7 carbon atoms (for example, vinyl methyl ket.one, vinyl ethyl. ketone, and vny.I. hutyl ketone), etc. These polymerizable unsaturated monomers may be used singly, or in a cowbinat.xon of two or more.
In terms of DCI and water resistance of the resulting coating film, it is preferable that the monomer component (I) at least part [ally include a hydroxy-containing polymerizab.].e unsaturated monomer. Specifically, it is preferable that the -1.5 polymerizahie unsaturated monomer (b) dl.iferent. from the C4--C24 alkyl-contain.inq polymerizable unsaturated monomer (a) at least partially include a hydroxy-conuannq polyinerizabie unsaturaned tnonome r.
The hydroxy-containing polwnerizahl.e unsaturated monomer may be, for exaule, those exemplified above in conjunction with the polymerizable unsaturated monomer (h) that is different from the C4--024 alkyl containing polymerizable unsaturated monomer (a) These monomers may he used singly, or in a combination of two or: more.
Preferable as the hvdroxv-containing polymerizable unsaturated monomer are 2--hydroxyethy.1 (xneth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4 hydroxyhutyl (meth) acry.l ate.
When contained in the monomer component (I), it is preferable that the hydroxy-containing polymerizable unsaturated monomer be used In 5 to 60 mass%, preferably 10 to 45 mass%-, further preferably 15 to 30 mass%, based on the total mass of the monomer: component (I), in terms of DOT and water resistance 2.0 of the resulting coating film.
Further, when the monomer component (I) contains the hydroxy-containi.ng po.l.ymerizabie unsaturated monomer, it is pthfdrable that the polymer obtained by polymerizing the monomer component (1) have a hydroxy value of 2Oto 260 tog KOH/g, preferably 40 to 200 mg K(H/g, fur her preferably 60 to 130 tag KOH/g, in tenns of 001 and water resistance of the resulting coating film.
Macromonorner (rni) The macromonomer (rn-U includes a polymer chain and a polymerizahie unsaturated group. The polymer chain is a polymer chain having a number average molecular weight of 1,000 to 1.0, 000 obtainable by polymerizing the monomer component (I) that contains the C4-C24 alkyl.--containi.nq poiymerizah.le unsaturated monomer (a) in the present invention, the. rmacromonomer is a high-molecular--weight monomer having a polyrnerizable unsaturated group, prefezably at the polymer end. That is, the macromonomer (rn-i) is structured to include a polymer chain backbone, and at reast one preferably one polymerizable urtsaturated group, preferably at the end of the polymer chain, s used herein, the polymerizahie unsaturated group contained in the macromonoirer (m-l) means an unsaturated group that can undergo radical polymerization. Examples of such polymerizable unsaturated groups include a vinyl group, a vinylidene group, an acryloyl group, and a methacryloyl group.
The macromonorner (rn-i) preferably has a number aver.age molecular weight of 1,000 to lO,l00 in terms of WI of the resulting coating film, a number average molecular weight of 1,000 to 5,000, more preferably 1,000 to 3,000 is preferable.
The number average molecular weight of Lhe macromonomer (rn-i) can be adjusted by, for example, the amount of chain transfer agent, the amount of-radical polymerization initiator, reaction temperature, and reaction time used for the polymerization of the monomer component (I) -The zracroinonomer (n-i) can he obtained by methods known per se. Specifically, for example, the following methods (1), (2), and (3) can be usea.
Method (1) The monomer corponent (I) is polyrnerized in the presence of a chain transfer agent that contains a first cheni.cal.iy reactive group such as a carboxy group, a hydroxy group, an amino group, etc., so as to introduce the first cherrdcal Thy reactive group a** the polyer end. The polymer is then allowed to react with a polymerizable unsaturated monomer that has a second chemically reactive group that can react with.
the first chemically reactive group of the polymer, so as to obtain the rnacromonomer (m-1) -For example, mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 2--mercaptoethanol, . and 2-aminoethanethiol can be suitably used as the cha:i.n transfer agent that has tre first chemically reactive group such as a carhoxy qrouv, a hythoxy group, an amino group, etc. The polymerizable unsaturated monomer having the second chemically reactive group that reacts with the.fi±st chemically reactive crour' in the copolymer to introduce the poyrnerizabie unsaturated group may preferably be, for example, an epoxy-containing plymeri.zable unsaturated moncsne:r: when the first chemically reactive group is a carboxy group, an isocyanato--containing polymerizable unsaturated monomer when the first chemically reactive group is a hydroxy group, or an epoxy--containing polymerizable unsaturated monomer when the first chemically reactive group is an amino group.
For exarrple, g].ycidyl acrylate, c.iycidyl rrethacrvlate, etc.., can be suitably used as the epoxy--containing polymerizable unsaturated monomer. Further, for example, isocyanatoethyl acrylate, isocyanatoethyl methacrylate, m-isopropenyl---a,a---dimethyl henryl isocyanate, etc., can be suitably used as the i.socyanato-containing pol.ymerizable unsaturated monomer.
Method (2): The macromonomer (rn-i) can be obtained by catalytic chain transfer polymerization (CCTP method) that uses a metal complex. The CCTP method is described in, for example, Japanese Unexaiiüned Patent Publications No. 1994-23209, l95-3541l, 1997W 501457, 1997-175256, and Macromolecules 1996. 29, 8083 to 8089.
Specifically, the macromonomer (rn-i) can he produced by the catalytic chain Lransfer polymerization of the monomer component (I) i.n the presence of a metal complex. The catalytic chain transfer po.lyertzation can be performed using, for example, a solution polymerization method i.n an organic solvent, or an emulsion oolymerizs ion method In water. s retT1ired, a radical.
polymerization initiator may he used f:or the polymerization, in addition to the metal. complex.
Examples of the metal complex include a cobalt complex, art iron complex, a nickel complex, a ruthenium complex, a rhodium complex, a palladium complex, a rhenium complex, art -.i0.
iridium complex, etc. The cobalt complex efficiently exhibits the catalytic chain transfer effect. The amount of. metal, complex used is not particuLarly limited, and is generally 1 x 10" to 1 part by mass, pteferably 1. x l0 to 0.3 parts by mass, based on the total 100 parts by mass of the monomer component (Tj.
Examples of the radical polymerization initiator include: organic pe.roxide.s such as bens'oyl peroxide, octanovi per xide, lauroyl petoxide, stearoyl peroxide, cumene hydroperoxide, tert-butyl peroxide, di-tert--amylperoxide, tert-- butylpe.roxy--2--ethylhexanoate, tert-butyiperoxy laurate, tert-hutyIp roxy isopropyl carbonate, tert---hutyiperoxy acetate, dilsopronyibeuzene hydroperoxide, etc.; azo compounds such as azohi.si.sohutyronitriie, azobis (2, 4-dirnethylvaleronitrile) azohis (2-tnethylproionitri le), azobis(2---methylhutyronitriie) 4,4' -azobi.s (4-cyanobutanoic acid) , dimethyl azob:Ls (2-methyl propionate). azohi.s (2 --methyl--N--(2-hydroxyethy.l -propi.onai.idej azobis (2-methyl-N--[2-(1-hydroxybutyl) ] -propionamide} * etc.; and persui.fates such as potassium persuifate, almeriium persuit.ate, sodium persulfate, etc.. These polymerization initiators may be used singly, or in a combination of two or more. The content of the rathcai oiymerizaticn initiator is not particularly limited, and is generally 01 to 10 parts by mass, preferably 01 to B parts by mass, further preferably 0.1 to 6 parts. by mass, based on the total 1.00 parts by mass of the monomer component (1).
Method (3): The macromonomer (rn-i) can be obtained by additIon-fragmentation chain transfer po1yneri.zation that uses an addition-fragmentation chain transfer aaent. Addition-fragmentation chain transfer poi.yr:eri.zation is described in, for example, Japanese Unexamined Patent Publication No. i995-2954 Snecifically, the macromonomer (rn-i) can be produced by the addi.tion-f.racxmentat.ion chain transfer polymerization monomer component (I) in the presence of an addition-fragmentation chain transfer agent. The addition-traqmentation chain transfer polynterizs.tion can he performed usi.ng, for examo1e a solution polymerization method in an organic solvent, or an emulsion po*lcaeri.zati.on metnod in. wate.r As required, a radical polymerization initiator may he used for the polymerization, iii addition to the addition-fragxtantation chain transfer acent, For example, 2, 4-dipheny1--4-methyF--1-pentene V'a-methyi styrene dimer", also known as MSD") can he suitably used as the additionfragmentation chain transfer agent. The content of the addition-fraqmentation chain transfer agent is not particularly limited, and is generally 1 to 20 parts by mass, preferably 2 to parts by mass, further preferably 3 t.o 10 parts by mass, based on the total 100 parts by mass of the monomer comDonent (I) The radical polymerization initiator mentioned in method (2.) above, for example, nay he used as the radical.
polymerization initiator. The polymerization initiators may be used singly, or in a cottination of two or more. The content 01 the red joel. pol.wner.i.zat.JMn initiator: is not particularly limited, and is generally 1 to 20 parts by mass, preferably 2 to 15 parts by mass, further preferably 3 to 10 parts by mass? based on the total 100 parts by mass of the monomer component (I).
In these methods (1) to (3), although the polymerization temperature varies depending *on the type of. the radical polymerization initiator, the polymerization temperature is preferably in a range of from 60 to 200 C, more preferably from 0 to 1@0C, further preferably from 90 to l70C Further, different temperatures may be used in the first half and the second half of polymerization, or polymerization may be performed with gradual changes in temperature.
Of th.e above methods (1) to (3), method (1) requires the step of polymerizing the monomer component (I) to obtain a polymer, arid the step of reacting the polymer with a polymerizabl.e unsaturated monomer to Introduce a polymerizabie unsaturated group into the polymer Method (2) uses a metal complex, and thus catalytic chain transfer polymerization may occur during the production. of the copo.ymer (gi.aft polrer) described later, or color may be imparted to the resulting copoiwner Thus, in terms of reducing the rius±er of reaction steps S and suppressing the coloring of the resulting copolymer, it. is preferable to obtain tiie rnacromoriomer (rn-i) using method (3) which uses the addition--f raqmentation chain transfer polymerization using an addition---fragmentation chain transfer agent. The macromonomer (rn-i) can be used singly, or in a combination of two or more.
Fk I rne-4ut Un t uhatud &norer tonL-ainLs Hydtohflc Cr up In. the present invention, examples of polyinerizable unsaturated monomer (m-2) containing a hydrophilic aroup include N--substituted (moth) acrylanilde, polyrnerizable unsaturated monomer having a p-olyoxyal kylene chaTn, N-vinyl---2--pyrro1idone 2--hydroxveLhyi acrylate, carboxy-containing polvmerizable unsaturated monomer, sulfonic acid group-containing polymerizable unsaturated monomer, and phosphoric acid group--containing polymerizahie unsaturated monomer. These monomers can he used s3ng.ly, or i.n a combination of two or more.
Miong them, the poi.ymeri zahie unsaturated monomer containing a hydrophilic group (m-2) may be, for example, at.
least one kind of polynieri.zable unsaturated monomer selected from the group consisting of N-substituted (meth) acrylamide, polymerizable unsaturatd monomer having a polyoxyalkylene chain, N-vinyl-2pyrrolidone, 2hydroxyethyl acrylate-, acrylit acid, and methacrylic acid. These may be used -singly, or in a conujinatlon of two or mere.
in terms of the smoothness DCI, luster, and water resistance of the result-ing coating film, the contents of -the macromonorner (rn-I) and the polyrnerizable unsaturated monomer containing a hydrophilic group (m-2) in the monomer component (m.) preferably fai.i within the ranges-below, based on the total mass f the monomer component (in) Macromonomer (ml) I to 40 mass%, preferably 3 to 29 mass%, further preferably 5 to 15 mass%, Folvmeri zahl.e unsaturated monomer contái fling a hydrophilic group (m-2): 5 to 99 nass%, prefetably 10 to 97 mass%, further p'efeLably 20 to 95 mass%.
Examples of the Nsubst.ituted (math) ac.rylamide include N-methyl acrylancide, N-methyl methacrylarcade, N-methylol acryi.amide butyl ether, N-methyi.ol methacrylaxni.de hutyl. ether, N-ethyl -cry±amide, N-ethyl methacrylamide N-n--propyi acrylamide, N-n-propyl methacrylamide, N-isopropylacrylamide, N isopropyl methacrylamide, N--cyclooropyl acryIamide N--P cyclopropyl methacrylamide, diacetone acrylamide, diacetone methacrvlamide, N-hydroxrethyl acrylamide, N--hydroxymethyl meth.acrylamide, N-hydroxyethyl acrylanide, N-hydroxyethyl rnethacrylamide, N,N---dimethyl acrylamide, N,N-d.tmethyl methacrylamide, N, N-die thyl acrylamide, N, Ndiethyl methacrylamide. N-methyl, N-ethyl acrylamide, N-methyl, N-ethyl methacrylanilde, N,N-dimethv.iaminopropyl acrylathide, N,N-dimethylaminopropyl methacrylamide, N-methylol acrylamide methyl ether, N-me t.hyloi methacrylarcdde methyl ether, N-methylol acrylamide ethyl ether, N-methylol methacrylamide ethyl ether, N'-methyloi acrylamide propyl ether, N-methylol methacrylamide propyl. ether, acryloyl morpholine, and methacryloyl inorpholine.
These may be used singly, or in a combination of two or more.
In terms of DCI of the resulting coating film, N-n-propyl acrylamide, Wn-propyl methacrylamide, Wisopropyi acrylamide, N-isopropyl. Inethacrylathide, N-hydroxyethyl acrylamide, N-hydroxyethyl methacrylamide, N,Ndi.methy1 acrylarn.ide, N, N-diinethyl methacrylamide, N, N-diet.hyl acrylamide, and N,N-diethyl methacrylami.de are preferred, and N,W-dtmethyl acrytamide and N, N-dimethyl methacrylamide are further preferred.
The polnerizable unsaturated monomer havin; a polyoxyalkylene chain is a monomr that includes a polyoxyalkylene chain and a polymerizable unsaturated group per molecule.
Examples of the polyoxyalkylene chain include a pol.yoxyethyiene chain, a polyoxypropylene chain, a chain that includes a polyoxyethylene block and a polyoxypropviene block, and a chain that includes randomly linked polyoxysthylene and polyoxypropylene. The polyoxyalkylerie chain preferably has a molecular weight of generally about 100 to 5,000k preferably about 200 to 4,000, further preferably about 300 to 3,000.
A representative example of the polymerizah.l.e unsaturated monomer having such. a po1yoxa1kyl.ene chain is, for example, a polymerizable unsaturated monomer of General Formula (I) below. R1 0
H2C=_:ll4O_R3}0_R2 (1) wherein R represents a hydrogen atom or a methyl arouo; K2 represents a hydrogen atom or a 01-C4 alkyl group, preferably a hydrocen atom, a methyl group, or an ethyl group, further prefeahl.y a hydrogen atom or a methyl. group; P3 represents a 02 04 alkylene group, preferably a 02 or 03 alkylene group5 further preferably a 02 alkylene group; and in is an integer of 3 to 150, preferably 5 to 130, further preferabl.y S to 50. In General Formula (14, in oxyalkylene units (0-Rb may be the same or different.
specific exampies of the poiiaerizable unsaturated monomer represented by General Formula (1) include tettaethylene glycol (meth)aczylate, methoxytet.raethylene gl.yco! (met acrv.late. ethoxytetraethylere glycol (meth) acrylate, n-hut.oxytr iet.hylene glycol (math) acrylate, E-i--butoxyt.etrae-thylene qlyool (meth)acryiate, tetrapropylene gl.ycol (meth) acryi.ate, methoxytetrapropylene glycol (meth) acrylate, ethoxvtetraoropylene alycol (meth) acrylate, butoxyt.etrapropylcne glycol (math) ac.rylate, pn.yethyi.ene glycol (meth) acrylate, . coiypropvlene glycol (meth) acrylate? polyetk ylene (propylene) glycol (meth)acrylate, S methoxypoiyethvlene glycol (math) acrylate, ethoxypolyethy].ene gi ycol (math) acrylate, methoxypolyoropylene gi.ycol (math) acrylate, ethoxypolypropylene glycol (math) acrylate, methoxypolyethyi.ene (propylene) glyco]. (math) acrylate., and ethoxypolvethylene (propylene) glycol (math) acrylate, These may he used singly, or in a combination of two or r,ore. As used herein, "polyethylene.(propylene) glycol" means a coo1ymer of ethylene glycol and propylene glycci, including both a block copolymer arid a random copolymer.
in he ins of DO' of the resulting coating film, polyethylene glycol (meth) acrylate, polyethylene (propylene) g.iycol (math) acrylate, methoxypolysthylene glycol (math) acrylate, and methoxypoi.yethylene(propylene) gi.ycol (meth)acryi.ate are preferable, and polyethylene rjlycol (neth)acrylate and methoxypolyethylene glycol (math) acrylate are further preferable.
The polneri.zable unsaturated monomer havJ.ng the po].yoxyalkylene chain preferably has a molecular weight of generally about 300 to 6,000, preferably a:bout 400 to 5,000.
further preferably about 450 to 3,500.
Examples of the carboxy-containing polymerizable unsaturated monomer include (meth)acrylic acid, maleic acid, crotonio acid, and B--.carboxy ethyl acrylate. They can be used singly, or in a combination of two or more.
Examples off the sul foni.c: acid group-containing po.1.ymerizahle unsaturated monomer include 2acrylanide-2-methylpropanesulfonic acid, 2-sulfoethyl (meth) acrylate, allyl sulfonic acid? arid 4-styrenesulfonic acid; and sodium salts and aipmonium salts of t.hee suifonic acids. They can he used singly, or ir of two or more.
Examples of the phosphoric acid group-containing polymeri:ahle unsaturated monomer i.n ude 2-acryloy]. oxye.thyi.
acid phosphate, 2-methacryloyioxv ethyl acid phosphate, 2-acryloyloxy propyl acid phosphate, and 2--inethacryloyloxy nronyl acid phosphate. They can he used singly; or in a combination of two or more.
In a preferred embodiment of the present invention, the polymerizabie unsaturated monomer containing a hydrophilic group (m-2) may be, for example, at least one kind of: hydrophilic grouD-contairiino nonionic nolvmerizable unsaturated monomer selected from the group consisting of N-substituted (meth)s.cryl.amide, a polyrnerinbie unsaturated mononer having a polyoxyalkylene chain, and N-vinyl-'2-pyrrolidone. These way he used singly, or in a combination of two or more. In a preferred embodiment of the present invention, N--substituted (meth)acrylamide is preferable among these monomers, in terms of 001 of the resulting coating film.
In a preferred embodiment of the present invention, the macrornonomer (rn-I) and the nonionic polymerizahi.e unsaturated monomer containing a hyd.roph to group (m 2) are preferably contained in the proportions below, based on the total mass of the monomer component (in), in terms of the viscosity of the copolymer, and 001 of t:ne coating film formed by using the copolymer-containing coating composition.
Macromonomer (rn-i): 1 to 29 nass%, preferably 3 to 20 rnass%, further preferably S to 15 mass% The total mass of the nonionic polymerizable unsaturated monomer containing a hydrophilic group (m-2): 20 to 99 mass%, preferably 40 to 97 mass%, further preferably 55 to mass%, in another preferr-d embodiment of the. .present invention, the polymerizabte unsaturated monomer containing, a hydrophilic group (n-2) may be at least one kind of polymerizahle unsaturated monomer selected from acrylic acid and mathacrylic acid. These may he used s.ngly, or in a combination of two or more. In another preferred enthodiment of the present invention, acrylic acid is preferable among these monomers, in terms of 001 of the resulting coating film.
In another preferred embodiment of the present.
invention, the rnacromonomer (rn--i) and the poiynerizahle unsaturated monomer containing a hydrophilic group (m-2) are -preferably contained in the proportions below, based on the total mass of the monomer component (in) , in terms of-the vscosity of the copolymer, 001 of the cc: tinq film formed by using the copolymer-containing coating composition, the improvement of flip--flop property and water resistance, and the -suppression of metallic mottling --Macromonomer (i-i) 1 to 40 mass%, preferably 3 to 2.9 mass%, further preferably 5 to 15 mass% The total -mass of poiymerizable unsaturated monomer containing a hydrophilic group (m---2) S to 75 irass%, preferably 10 to 60 mass%, further preferably 20 to 50 mass.
Other poiymerizable unsaturated monomers (m-3) are polymerizahle unsaturated monomers other than the necromonother Cm-i) and the polymaerizable unsaturated monomer containing a hydrophilic group (m-2) The other poiyinerizabie unsaturated monomers (im--3) can be suitably selected according to the properties required of the copolymer.
Specific examples of the other poi.ymeri.zable unsaturated monomers (m-3) are listed below. These may be used singly or in a combination of two or nK>re. - (i) Alkyl or cycloalkyl (rneth)acrylates: methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (math) acryLte, iso--propyl (meth) acrylate, n---butyl (moth) acrylate isc---butyl (meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, n--octyi (meth) acrylate, 2---ethylhexy].
(math) acrylate, nonyl (math) acrylate, tridecyl (math) acrylate, Iauryi. (meth) acrylate, stearyl (meth) acrylate, isostearyl (meti-i) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (math) acrylate, tert-butylcyclohexyi (math) acrylate, cycl.ododecyi. (meth) acrylate, t:i.cyclodecany]. (mc-th) acrylate, ecu (ii) Polymerizable unsaturated monomers having an isohornyl. group: isobornyl. (meth) acryl.ate, etc. (iii) Polymerizable unsaturated monomers having an adamantyi group: adamanty.l (meth)acrylate, etc. (iv) ?clymerizabie unsaturated monomer having a tr:icyclodecenyl group: tricyclodecenyl (math) acrylate, etc. (v) Aromatic ring-containing polymerizable unsaturated monomers: benzyl (moth) acrylate, styrene, a-methyl styrene, vinyl toluene, etc. (vi) Polymerizabie unsaturated monomers having an alkoxysilyl group: vinyit.ri.methoxysilane, vinyltr.iethoxysilane, vinyl.tri.s (2--methoxye.thoxy) silane, y-(moth) acriovi oxvpropyltrimethoxys].lane, y-(meth)acryloyl oxypropyltriethoxysiiane1 etc. (vii) Poiwnerizabie unsaturated monomers having a fluorinated alkyl group: perfluoroalkyl (moth) acrylates such as perf.i.uorobutylethyl (meth)acrylate and perfiuorooctyiethyi (meth) acry.late; fluoioolefin; etc. (viii) Polymerizable unsaturated mononar having a photopolymerizable functional group, such as a maleimide group et.c (ix) Vinyl compounds: ethylene, butadiene, chiorocrene, vinri propionate, vinyl acetate, etc. (x) Eydroxy-containi.ng polymer.izahie unsaturated.
monomers; monoesterified products of (meth)acrylic acid with a dihydric alcohol, having 2 to 8 carbon atoms (eg., 2- hydroxyethyl methacrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (math) acryl.ate, and 4-hydroxyhutyl (moth) acryl.ate); s-caprolactone modified products of the monoesterified products of (meth) acrylic acid with a thhydric alcohol having 2 to B carbon atoms: allyl alcoho]., etc. (xi) Nitrogen-containing polymerizabie unsaturated monomers; (moth) acryi.onitrt.le, (moth) acrylami.de, niethylene his (meth) acrylamide, ethylene his (meth.) acryl.amide, 2- (methacrylcyloxy) ethyl. t.ri.methyi arnmoniuxn chloride, and adducts of q.lycidyl (meth) acrylate with amine compounds, etc. (xii) Poiyme.r:i.zable unsatux:ated monomers including at least two poiym.erizahie unsaturated groups per. iecui1e: al.i.yl(rueth)acrylate, I, 6-hexanediol di{meth)acrylate, etc. (xiii) Epoxy-containing polymerizable unsaturated monomers: glycidyl (math) acrylate, --methyi.giyc.idyl (math) acrylate, 3, 4-epoxyc.vclohexylmethy1 (math) acrylate, 3 1-epoxycycl.onexylethyi (meth acrylaLe, 3, 4epoxycyciohexy1propyl (meth)acrylate, ailyl glycidyl ether, etc. (xiv) Pal ymeri zabte unsaturated monomers including a ultraviolet-absorbing functional group: 2-hydroxy-4--(3-- methacryloyloxy-2-hydroxypropoxy) benzophenone 2--hydroxy--4---(3-- acryioy1oxy-2--hydroxypropoxy) benzophenone, 2,2 -dihydroxy--4---(3- methacry1oyloxy-2-hydroxypropoxy) benzophenone, 2 * 2 --dihvdroxy-4- (3-acryioyloxy-2-hydroxyiropoxy) benzophenone, 2-(2 -hydroxy--5t methacryloyloxyethylphenyl) ---2H---henzotriazole, etc. (xv) Light-stable polymerizatle unsaturated nionomers: 4-. (math) acryloyioxy-1, 2,2, 6, 6-pentamethylpiperidine, 4- (math) acryloyi.oxy-2, 2,6,6 tetramethyl.pieridine, 4-cyano-4- (math) acryloylamino-2, 2,6, 6-tetramethylpiperidine, l (math) acryl.oyt-4-(math) acrvloylanthio-2, 2,6,6- tetranethylpiperidine, 1-(math) acryloyl-4-cyano--4- (math) acrylovlamino-2, 2,6, 6-tetranethylpiperidine, 4- crotonoy.ioxy-2,2, 6, 6-tetramethylpiperidine, 4-crotonoylamino- 2 2, 6, 6--tetrarnethyipiperidine, 1-crotonoyl -8--crotonoyloxy-- 2,2, 6, 6-tetramethylpiperidine, etc. (xvi) Poimerizable unsaturated monomers having a carbonyl group: acrolein, diacetone acrylamide, diacetone 3D methacr yla -.ide, acetoacetoxylethyl methacrylate, fonnyistyrol, vinyl alkyl ketone having 4 to 7 carbon atoms (for example, vinyl methyl ketone, vinyl ethyl ketone, and vinyl butyl ketone) etc. (xvii) Polymerizable unsaturated monomers having an acid anhydride group: maleic anhydride, itaconic anhydride citraconic anhydride etc. when the po.i.vme.ra.zanle unsaturated monomer (n-2) having a hydrophitic group does not contain 2-hydroxyethyi acrylate, it is preferable that the pol.nerizabl.e unsaturated monomer Cm 3) at least oartial.lv include the hydrozy-conLaininu colymerizable unsaturated tronomer (x) , in terms of the water resistance of the resulting coating film. Preferable exalrcies of the hydroxy- containing polymer i.zahl.e unsaturated monomer (x) Include 2-- hydroxyethyl methacryi.ate, 2--hydroxynropyl (meth) acryl.ate, 3-hydroxypropyl (meth acrylate, and 4-hvdroxybutvi (meth) acrylate, of which 2hydroxyethyl methacrylate is preferred.
When the polymerizable unsaturated monomer (m-3) contains the hydroxy---containing polymerizable unsaturated monomers (x), it is preferable that the content ofte hydroxy- 1.5 containing polymerizable unsaturated mononer (x) haS to 79 rnas% preferably 10 to 57 mass%, further preferably 15 to 40 mass%, based on the. total. mass of the monomer component. (m) The content of the po±ymerzah1e unsaturated monomer (m--3) can he suitably set so as to make the total wegnt of tne (rn-i) component and the (m--2) component in monomer component (in) 1.00 mass%.
A copolyrner of the present invention is generally a graft polymer having a main chain and aside chain. The side chain portion is formed by the polymer chain in the macromonomer (rn-i). The main chain portion is formed by the polyterizable unsaturated monomer containing a hydrophilic group {m-2) , and the polymerizable unsaturated monomer (m--3).
cR.y:roauo:mnoca copolymer of the present invention can be produced by copolymerizing the monomer component (in) that includes the nscromonomer (m-l) , the polymerizabie unsaturated monomer containing a hydrophilic group (m---2), ande optionally the potymerizahie unsaturated monomer (m-3) ; using methods known per se,such as, for example, a solution polymerization method in an organic solvent * and an emulsion polymerization method in. water etc., of which the solution polymerization method is preferable because of the relatively easy procedures it offers.
Examples of the polymerization initiator used for the copolymerizati.on of the monomer component (m) include: organic peroxides such as benzoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, curnene hydroperoxide, tert--butyl peroxide, ditertamylperoxide, tert--buty1peroxy--2-ethylhexanoate, tert-butylperoxy laurate, tertbuty1peroxy isooronylcarbonate, tert-butylperoxy acetate, diisopropylbenzene hydroperoxide, etc; azo compounds such as azobisisobutyronitrile, azobis (2, 4-dimethylvaleronitrile), azohis (2-iuethylpropionitrile) , azobis (2-methyl. hutyronit rile) 44-azobis(4--cyano butanoic acid), dflnethyl azob±s(2inethyi propionate), azohis [2-methyl--N--(2-hydroxyethyl) -propionamide], azobis*f2-methyl--t[2-(1--hydroxybuty1) ]-propionamide etc; and pe.rsultates such as potassium persulfate, ammonium persuifate, sodium persulfate, etc. These polymerization initiators may he used singly, a combination of two or more. Redox initiators prepared by combining a polymerization initiator as mentioned above with a reducing agent such as sugar, sodium formaldekydesulfoxylate, iron complex, etc, may also be used, as required.
The amount of polymerization initiator used may he generally 0.01 to 5 parts by mass, preferably 0-i to 3 parts by mass, based on the total 10:0 parts by mass of the monomer component (m) The method of adding the polymerization initiator is not particularly limited, and can be suitably selected according to the type and amount of the polymerization initiator used. For example, the polymerization initiator may be incorporated into a mononer mixture or a reactioo solvent beforehand, or may be added dropwise or all. at once at the tine of polymerization.
Water-soluble organic solvents that do not easily cause chain transfex: into the solvent are preferably used as the solvent for the solution polymerization method. Examples of such solvents include ester--based solvents such as ethylene olycoi.
monomethyl ether acetate, diethylene glycol monobutyl ether acetate; ketone-based solvents such as acetone or methyl ethyl ketone; alcoholic solvents such as methanol, ethanol, o J.soproparAoi., n-butancl, sec-butanol, or isobutanol; ether-based solvents such as 1, 4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene clycol dirnethyl ether, propylene glycol dimethyl ether,. or dipropy].ene glycol dimethyl ether; and glycol ether-based solvents such as ethylene glycol ruonomethyl :io ether, ethylene glycol monoethyl ether, or ethylene glycol monobutyl ether. These may be usea Slfl9iY, or in a combination of two or more.. Ether-based solvents and glycol ether-based solvents are preferable.
It is preferable that the amount of the organic solvent 1.5 used for the polymerization reaction he generally 500 parts by weight or less, preferably 50 to 400 parts by weight, further preferably 100 to 200 parts by weight, based on the total 100 parts by mass of the monomer component (m).
It is preferable that the copoi3naer of the present invention have a weight average molecular weight of 20,000 to 1,0001000, preferably 50,000 to 600,000, further preferably 100,000 o 400, 000, in terms of the thickening property u the resulting copolymer, and smoothness, 001, and luster of the coating film formed of the coating corrposition containing the copo].yxcer.
In this specification, the number average molecular weight of the ncromonomer (m-l), and the weight nieraae molecular weight of the copolymer are converted values relative to the molecular weights of polystyrene, obtainable by converting the measured gel permeation chromatograph (GfC) retent ion time (retertion volume) using the retention time (retention volume) of the standard polystyrene of a known molecular weight measured uitder the seine conditions.
The number average molecular weight of the macromonomer (rn-I) can be measured using an HlC8l20GP0" gel permeation chromatography apparatus (trade name; produced by Tosoh Corporation) together with the iour coims TSKge1 C-4000 HXL", "TSKgeI G-3000 HXT.", "TSKgeI G-2500 HXL" and "TSKge]. G-2000 HXL" (trade names; produced by Tosoh Corporation) and a differential refractometer as a detector under the following conditions; mobile phase, tetrahydrofuran; measurement temperature, 40°c; and flow rate, I rL/mi.n, The weight average molecular weight of the copolymer can he measured using an HLC-B12OGPC gel permeation chromatography apparatus (trade name; produced by Tosoh Corporation) with a TSKge.1. GiHR-L column (trade name; produced by Tosoh Corporation), and a differential refractometer as a detector under the following conditions: mobile phase, N, N-dimethyLformamide (containing 10 n lithium bromide and 10 mM phosphate); measurement temperature, 25°C; and flow rate, 1 mfjmiri.
A copolymer of the present invention has the characteristic of easily developing viscosity, and lowering its viscosity with an increase in rate of shear. This viscosity characteristic enables the copoiwner to he suitably used as a viscosity-control1ing agent for aqueous coating compositions.
Further, the copolymer has the characteristic of developing viscosity, and lowering its viscosity with an increase in rate of shear even in an aqueous coating composition that contains a surfactant. Thus, an aqueous coating composition containing a copoler of the present invention can form a coating film that has suerior 001. Further, with an aqueous coating composition of the present.. nvent.ion a coating film having superior luster with a high flip-flop property and suppressed metallic mottling can be formed.
An aqueous coating c:ompoamt on of the present invention (hereinafter, also referred to as the present coating composition") generally contains the copoi.ymer and a fi. 1st-forming resin (A) Resin (A) Water--soluble or water--dispersibi.e film--forininu resins known per se and used as t:te binder componenr of aqueous S coating compositions, can be used as the film-forming resin (A)-Examples of fulm-forming resin (A) include acrylic resin, polyester resin, alkyd resin, silicon resin, fluororesin, epoxy resin,; and polyurethane resin.
The fun-forming resin (A) is preferably a water-- dispersible film-forming resin, because film-forming resins enable formation of a coating film that has superior appearance with excellent EK}l, high flip-flop property, and suopressed metallic mottling, and excellent water resistance.
Water-dispersible film-forming resins are generally obtained by lz oispersng a relat jvelv h-urouhoni.. iiFt-±urnung resin in an aqueous medium, tnus enabi.ing ronnat ion or a coating ni.m that has superior water resistance compared with highly hydrophilic water-soluble film-fanning resins. Further, because of the hydrophobic side chain, a copolymec of the present in-er* ion can develop viscosity by forming a network structure with the relatively hydrophobic film-fanning resin, thus enabling i:ormatxon of a coating film that has superior appearance with excellent WI, excellent flip-flop property, and suppressed-metallic mottling.
In terms of the preservative stability of the resulting coating composition, the water-dispersible film--forming esin is preferably a film-forming resin that is rendered water--dispersible by a surfactant. A copolymer of the present invention has the characteristic of developing viscosity,-and lowering its viscosity with an increase in rate of shear even i.n an aqueous coating composition that contains a surfactant. Thus; the aqueous coating composition that contains a copolymer of-the present invention and the film--forming resin that is rendered water-dispersible by a surfactant can form a coating film that has excellent preservative stability; superior appearance with excellent DCI, h.iqn flip-lion property, anusuppressed metallic mottling; and excellent water resIstance.
For example, an acrylic resin produced by an emulsion polymerxzation methoc thd uses a surtactant can oe suitably used as the fiJin--forming resin that is rendered water--dispersible by a surfactant.
In terms of DCI, flip-flop property, and metallic mottling of the resulting coating film, the J lbs-forming resin (A) is peferably a resin that includes an ester bond, For example, a copolymer obtainable by polymerizing a monomer mixture that includes ester bond-containing polymerizah.l.e unsaturated monomers, acrylic resin, polyester resin, etc., can he suitably used as the ester bond-containing resin. Among them, acrylic resin is preferable. The aqueous coating compositiQn 1.5 that contains a copolymer of the present invention and the ester honci--cont.aini.ng f lxa-ifonr.ing resin can form a coating film that has superior appearance with excellent LtI, hIgh flip-flop property, and suppressed metallic mottling. PresuiMbly, this is because of the high viscosity developed by the formation of a networkst.ructure more strongly bonded togeth r by the high affinity between the ester bond in the film-forming resin (A) and the ester bond in the C4-024 alkyl-containing polymerizahl.e unsaturated monomer (a) present in the side chain of a coolx± of the present invention.
The filimformirg resin (A) preferably includes a cross.iinking functional group such as a hydroxy group a carboxy group, an epoxy group, etc. It is preferable that an aqueous coating composition of the present invention further include a curing agent (j3) *H0 be described later. When an aqueous coating composition of the present invention includes the curing agent (B), a resin (base resin) that has a crosslinking functional group such as a hydroxy group, a carboxy group, an epoxy group, etc., and that can form a cured coating by reaction with the curing agent (B) is qenerally used as the film-forming resin (A) Examples of the base resin include acrylic resin, polyester resin, alkyd resin, and polyurethane resin. The base resin is preferably a hydroxy-containing resin, -more prererably a hydroxy-containi.ng acrylic resin (Al) and/or a hydroxy-containing polyester resin (A2) In tones of improving DOl and luster of the resulting coating film, it is oreferable that the hydroxy-containing acrylic resin (Al) and the hynroxy-containing polyester resin (Th2) be used togetnen The content of the hydroxy-contain.ing acrylic resin (Al) li preferably about 20 to 80 mass%, particularly about 30 to 70 raass%, and the content of the hydroxy-containing polyester resin (A2) Is preferably about to 20 mass%, particularly about 70 to 30 mass%, based on the total amount of these resins.
When an aci.d group such as a carhoxy group etc. is contained, the filn'-fondng resin (A) has an acid value of preferably about S to 150 rug K0R/g, more preferably about 10 ho rag KOH/g, further preferably about 15 to 80 ng KOFI/g. When a hydroxy group is contained, the resin (A) has a hydroxy value of preferahl.y about 1 to 200 my KOH/g, more preferably about 2 to 180 rag KOH/g, furth r preferabi.y about 5 to 170 rug K0H/g.
*Hydroxy-Contaiüng_Acrylic Resin (Al The hydroxy-containi.ng acrylic resin (Al) can he produced by copolymerizing, for example, the hydroxy-containing polymerizable unsaturated monomer and other polymerizable unsaturated monomers copolynerizable with the hyd.roxy-containinq polnerizable unsaturated monomer, using methods known per se, such as, fo example, a solution poi.vnterizatiori method in an organic solvent, an emulsion polymerization method in water, a miniemulsion polymer.tzation method in water, etc. When the product is used as a film-forming resin for aqueous coating compositions, the emulsion polyerization method in water is preferable, because it requires fewer steps to produce the resin.
The hvdroxv-contairiing polymerizable unsaturated monomer is a compouna tnat includes one or more hydroxy groups 33 and one or more polymerizable unsaturated bonds per molecule, Examples of the hvdroxy-containinq polymerizable unsaturated monomer incnude: monoesteritiect products of metn) acryiic acad.
with a dihydric alcohol having 2 to 8 carbon atoms (eg, 2-hydroxyethyl (moth) acryl.ate, 2--hydroxypropyl (meth) acrylate, 3-' hydrcxyprooyl (math) acrylate, and 4-hydroxybutyl (meth) acrylate); -caprolacLone modified products of the monoesterifled products of (meth) acrylic acid with a dihydric alcohol having 2 to 8 carbon atoms; polyoxyalkylene glycol modified products of the monoesterified products of (math) acrylic acid with a dihydric alcohol. having 2 to B carbon atoms; N--hydroxynethyl (math) acrylamide; ally1 alcohol; and (math) acrylates that include hydroxy--ter.minated polyoxyethylene chains. These may he used singly, or in a combination of two or more.
Preferably, the hydroxy'-containing poiwner.izahle unsaturated monomer is a hydroxy-containing polymerizable unsaturated monomer having an ester bond, in terms of imnroving properties of the resulting coating film such as DCI, luster, fun--f lop property, etc, and suppressing metallic mottlins, Examples of such hydroxycontaining polymerizable unsaturated monomers having an ester bond include: monoesteri.fied products of (meth)acrylic acid with a dihydric alcohol having 2 to 8 carbon atoms (e.g., 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (nieth) acrylate, 3'-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth)acrylate); s-caprolactone modified oroducts of the monoesteri.fied products of (meth acrylic aci.d with a thhyonc alcohol having 2 to U carbon atoms; and polyoxyalky]ene g.lycc.i modified products of the ruonoesterified products of (moth) acrylic acid with a dihydric alcohol having 2 to 8 carbon atoms. Of these, monoesterified products of (meth)acrylic acid with a dihydric alcohol having 2 to 8 carbon atoms are preferable, and 2-hydroxyethy.l (math) acrv.Iate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4---hydroxyhutyl (math) acrylate are further preferred.
The other polym.erizahle unsaturated monomers -36-polymerizable with the hydroxy-containing polymerizable unsaturated monomer may be, for example, the. polymerizahie unsaturated monomers exemplified above as the (m-2) and (m--3) components in conjunction with the copolymer, including the polymerizable unsaturated monomers (I) to (ix) and (xi) to (xvii.) other than the hydmxy-containi.ng polymeri.zahle unsaturated monomer:. Such polymeri zahie unsaturated monomers may he used singly, or in a combination of two or more.
The hydrcxy---containing acrylic resin (Al) preferably contains an araide group. The hydroxy-containing acrylic resin containing an amide group can be produced by using, for example, an axaide-containinq polymerizable unsaturated monomer, such as (math) acrylamide, N, N-diLmethylamlnopropyl (meth) acrylainide, etc., as an example of the polymerizable unsaturated monomer polymerizable with the hydroxy-containing polymerizahie unsaturated monomer.
The content of the hydroxy-containing polynierizable unsaturated monomer used to produce the hydroxy-containi.ng acrylic resin (Al) is preferably about 1 to 50 mass%, more preferably about 2 to 40 mass%, further preferably about 3 to 30 mass%, based on the total amount of the monomer component.
In terms of properties such as the preservative stability of Lhe coating composition and the water resistance 01 the resulting coating film, the hydroxy-containing acrylic resin (Al) has an acid value of preferably about 01 to 200 mg KOH/c, more preferably about 2 to 150 mg KOH/g, and further preferably about S to 100 tug KOH/g. Further, in terms of properties of the resulting coating film such as water resistance, the hydroxy-containing acrylic resin (Al.) has a hydroxy value of preferably about 01 to 200 tug K0H/q, more preferably about 2 to 150 tug K0H/g, and further preferably about 5 to 100 tug KOH/g In a preferred embodiment of-the present invention, the hydroxy-containing acrylic resin (Al) may be a water-dispersible hydroxy-containing acrylicresin (Al') having an acid. value of I to 100 mg rc0i{/q and a hydroxy value of 1 to 100 Efi K01-1/g, .37.-.
obtainab).e by copo.ivmer:izing monomer components (b) that jnclude (b-i) 5 to 70 mass% of a hydrophobic polymerizable unsaturated monc'zner, (b-2) 01 to 25 mass% of a bydroxy-contai.ning polymerizabie unsaturated monomer, (b-3) 01 to 20 mass% of a carboxy-conta.i.ni.ng polymerizable unsaturated monomer, and (b--4) 0 to 94.8 mass% of a po1terizahie unsaturated monomer other thim. the ooi.vmerizabie unsaturated monomers (b-i) to (b-K)) By containing the above-mentioned water-dispersible hydroxyl containing acrylic resin (Al') in the coating composition as a hydroxy-containi.ng acrylic resin (Al) it i.s possible to form a coating fifln superior in b.ooLhnes, DCI and water resistance; moreover, when the coating composition further contains a luster p.iament, it is possible to form a coating fiflu having an excellent luster, with reduced metallic mottling and superior flip-flop property.
The hydrophobic poi.ymerizable unsaturated monomer (b--i) is a poiwnerizahi.e unsaturated monomer that has a linear, 2:0 branched? or cyclic, saturated or unsaturated hydrocarbon group of 4 or more carbon atoms, preferably 6 to 18 carbon atoms, excluding monomers having a hydrophi.lic group, such as, for example, hydroxy-containing polymerizable unsaturated monomers, etc. Examples of such monomers include alkyl or cycl.oai.kyl (math) acrylates such as n--hutyl (math) acrylete, isobutyl (math) acryl.ate, tert-butyl (math) acrylate, pentyl (math) acrylate, hexyl (meth) acrylate, octyl (math) acrylate, 2-et.hyihexyl (meth) acrylate, nonyl (math) acrylate, tridecyl (math) acrylate, lauryl (math) acrylate, stearyl (math) acrylate, Isostearyl (math) acrylate, cyclohexyl (meth) acrylate, methyl cvclohexyl (math) acrylate, terthutyl cyclohexyl (math) acrylate, cvciododecyl (neth) acrylate, tricyclodecanyl (meth) acrylate, etc -; polymerizable unsaturated compounds having an isohornyl group, such as isohornyl (meth) acrylate, etc.; polymerizahie unsaturated compounds having an adamantyl group, such as adamantyl (meth) acrylate, etc..; and aromatic ring-containing polvmerlsable unsaturated monomers such as benzyl (meth)acrylate, styrene. u---metnyi styrene. vinyl tc'luene, etc. These monomers rosy he used singly, or in a comhinat.on of two orrrjre, In terms of improving the smoothness, DCI, luster, and waterproofing of the resulting coating film, the hydrophobic polyrnerizabJ.e unsaturated monomer (h--i.) is preferably at least one kind of polymerizable unsaturated monomer selected from the group consisting of n-butyl (nieth) acrylate, 2-ethylhexyl (meth)acrylate, and styrene.
41!.±r The hydroxy-containing polymerizable unsaturated monomer (b--?.) improves the stability of the resu.itin.q waer--dispersible hydroxy-containing acrylic resin (A])) in an aqueous medium. Further, when using the comnound reactive with a hyciroxy group as the curing agent (B) described later, a coating film with superior water resistance can be formed in which the water-dispersible acrylic resin (Al') and the curing agent. (B) are crosslinked. The hydroxy--containing polymerizable unsaturated monomer (h-2) may be those described above.
oarboxy---contaiiunqPcaerizah.leunsauratedMonon(h) The carboxy-containing polymerizable unsaturated nonomer (h-3) can improve the stability of the resulting water--dispersible hydroxy--containing acrylic resin (Al') in an aqueous medium. When a compound reactive to a carboxy group is used as the curing agent (B) described later, a coating film with superior water resistance can be formed in which the water-dispersible hydroxy-containiriq acrylic resin (M' ) . and the curing agent (B) are crosslinked.
Examples of the carhoxy-contai.ni.ng poi.ymeri.zabie unsaturated monomer (h-3) include (meth)acrylic acid, maleic acid, crotonic acid, and -carboxyethy1 acrylate. These monomers may be used sincriv, or in a combination of two or more.
In view of enhancing the stàbilit' die resultinc water---dispers.i.oi.e nydroxy-containing acryltc resin (al' ) n an aqueous medium, the carhoxy-containhrig po.iymerizable unsaturated monomer (5-3) is preferably acrylic acid and/o.r methacrylic acid.
-\c ttenahle iatu:ted t o'cie-(t-4 ue' ___ Unsaturated Monomers (h--i.) to (h-3) The monomer component (b) may include, as required, a polymerizable unsaturated monomer (b--4) other than the hydrophobic polymerizable unsaturated monomer (b--i) the hydroxy--contai.n.inq po.iymenzable unsaturated monomer (b-2) , and the carhoxy-containing polymerizable unsaturated monomer (b-3), in addition to unsaturated monomers (h-i) to (b-3).
The polymerizable unsaturated monomer (b-4) can be suitably selected according to the properties required of the water-dispersible hvdroxy-containing acrylic resin (Al') -Specific examples of the nolymerizable unsaturated monomer (h--*4) are listed below These nay be used singly, or in a combination of two or more.
Examples of the polymer17 oble unsaturated monomer (b---4) include alkyl(meth)acrylates of 3 carbon atoms or less, such as methyl (meth acryl.aue, ethyl (meth) acrylate, n-propy.].
(meth) acrylate, isopropyl (meth) acrylate, etc; nitrc-rgen-containing polymerizable unsaturated monomers such as (meth) acrylonitri le, (math) acrylamide, methylene his (met-h) acrylamide, ethylene his (meth) acrylamide, 2- (methacryi.oyloxy)ethyl trimethyl axamoniusa chloride, and an adduct of glycidyl (neth) acry.iate with amine corrpoimds, etc; polymerizable unsaturated monomers that include at least two polymeri zahl.e unsaturated groups per molecule, such as aiIy.l (meth)acrylate, I, 6-hexanediol di(meth) acrylate, etc-; epoxy-containing pclymerizable unsaturated monomers such as glycidyl (math) acrylate, -methyilycidyl (math) acrylate, 3,4-epoxycyclohexyimethyl (math) acrylate, 3, 4-epoxycyc.lohexylethyl (math) acrylate, 3, 4-epoxycyclohexylpropyl (meth) acrylate, ally].
glycidyl ether, etc; (meth)acryiates having alkoxy-terminated polyoxyethylene chains and su].fon.ic aci.d group--containing polymerizable unsaturated monomers, such. as 2-acryiamide2-ruethyipropanesulfonic acid, 2-sulfosthyi (moth) acrylate, ailyl sulfonic acid, 4--styrenesuifonic acid, etc. , xnciuthnq sodium salts and ainmonium salts of these suifonic acids. These monomers may be used singly, or in a combination of two or more.
In terms of t-he smoothness, DOl, luster, and water resistance of the resulting cod*ing film, it is preferable that the hydrophobic polymerizable unsaturated monomer (h-1), the hydroxy-containing poi.ymertzahle unsaturated monomer (b-2), the carboxy-containi.ng polymerizable unsaturated monomer (b--3), and t.h.e po].ne.razabie unsaturated monomer (b-4) other than the polymerizable unsaturated monomers (b-i) to (b-3) he. contained.
in the monomer component (b) in the following proportions, based on the total mass of the monomer component (at) Hydrophobic po.lymerizahle unsaturated monomer (b-i): to 70 mass%, preferably 10 to 65 mass%, further preferably 15 to 60 mass% Hydroxy-containing polymerizabie unsaturated monomer (b-2) (Li to 25 mass%, preferably 05 to 15 mass%, further preferably 1 to 10 mass% Carhoxycontaining polymerizab.1.e unsaturated monomer (b-3) (Li to 20 nass%, preferably 05 to 15 mass% further preferably 1 to 10 mass% Polymer.i.zabi.e unsaturated monomer (h4) other than polymerizable unsaturated monomers (b-i) c, (b-3) o to 948 maset, preferably 10 to 139 mass%, further preferably 20 to 83 mass% The water-dispersible hydroxy-containing acrylic resin (Al') can be produced by, ifor example, copolnerizing the monomer component (h) that incudes the hydrophobic Polymerlzable unsaturated monomer (b-i) * the hydroxy-containing polymerizable unsaturated monomer (b-2), the carboxy-containing poiymer.i.zahl.e unsaturated monomer (h-3, and the polymerizable unsaturated monomer (b-4) .. other than the polymenizahie unsaturated monomers (b-i) to (b-3), using methods known per se.
Specifically, for example7 the ccpoi.yn r after emulsion polymerization, or after solution polymerization in an organic solvent may be dispersed in water using a surfactant. An emulsion polymerization method is preferable in terms of improving the stability of the resulting water-dispersible hydroxy-containing acrylic resin (Al') in an aqueous medium. The emulsion polymerization method is a method in which, generally, water-in5oluble or poorly water--soluble polymerizable unsaturated monomers are polymerized by being dispersed in water using a surfact.ant.
The water-dispersible hydroxy-containing acrylic resi.n (Al') prepared from the raw materials (b-i) to b-3) and, as required (b-A) preferably has an acid value of 1 to 100 rag KOH/g. and a hydroxy value of 1 to 100 ma K0H/q. The acid value is more preferably 2 to 50 mg KOi-i/g, further preferably 5 to 30 rag K0I-1/g, In terms of preservatrvestab.i1.ty of the. coating composition, and improving the smoothness, 001, luster and water reãistance of the resulting coating film. The hydroxy value i.e more preferably 2 to 80 rag KOH!g, further preferably S to 60 ma KOH/g, in terms of improving the smoothness, 001, luster, and water resistance of the-resulting coating film.
-.L..:s:.___ The hydroxy-containing acrylic resin (Al) is preferably formed of a water-dispersible hydroxy-containing acrylic resin used alone or in combination with a water-soluble hydroxy-containing acrylic resin; ir terms of improving 1101 and luster of the resulting coating film, Particularly, a -core-shell-type water-dispersible hydroxy---containing acrylic resin i.e suitable for the waterdispersible hydroxyccntaining acrylic resin.
A suitable exaioie of the core--she.fl type wate: dispersible hydroxy-containinq acrylic resin, in tents of mprova. ng 001 and luster of. the resuj.ting coating fiDn, is a core--shel i-type water-dispersih1 e hydroxy---containing acrylic resin (Al'' comprising: a core that is a copolymer (1) consisting of ahout 0.1 to 30 nass% of a polymeri.zable unsaturated monorer having two or more polvmerizabie unsaturated groups per molecule and about 70 to 99, 9 rnass% of a polymerizable unsaturated monomer having one polymerizah.l.e unsaturated group per molecule; and a shell that is a copolymer (11) consisting of about 1 to 40 mass% of a hydroxy--containing polymerizahl.e unsaturated monomer, about 5 to 50 mass% of a hydrophobic polymeri2abie unsaturated monomerç-and about 10 to 94 mass% of othe.r po.1.ymeri.zab.l.e unsaturated monomer(s) The ratio of copolymer (I) tocopolyner (Ii) i.e preferably in the range of. about 5/95 to 95/5, more preferably about 10/90 to 90/10, further preferably about 50/50 to -5/i5, parti.oul.arl.v preferably about 65/35 to 80/20, in tents of i.mproviru EC)I and 2.0 luster of the resuitng coating film.
Examples of polymerizable unsaturated monomers having two or mdre poi.ymerizable unsaturated groups per molecule, and that can he used as a monomer for the core copolymer (I) include allyl (meth) scrylate, ethylene glyco.1 di. (math) acrylate, triethyl.ene glycol di. (math) acrylate, tetraethylene glycol di (meth) acrylate, 1, 3-butylene glycol di (meth) acrylate, trimethy.Iol. propane tn. (math) acrylate, l,4-butanediol di (meth) acrylate,. neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (math) acrylate, pentaerythritol dJ (math) acrylate, pentaerythr.itol tetra(meth)acryi.ate, glycerol di(meth)acrylate, 1, 1, l-tris---hydrcxymethylethane di (meth acrylate, 1,1, l-tris-- hydroxyniethv.lethane tni(meth)acrylato, 1-1,1-tris---hydroxymethylpropane tn (raeth) acrylate, tniallyl isocyanurate, diallyl terephthalate, divinylbeazene, etc. Such monomers can he 33 used singly, or in a contination of two or more.
The pclnerizab1e unsaturated monomer having two or more polymerizable unsatura.ed groups per molecule functions to provide a crosslinked structure to the core copolymer (U A]. though the amount of the polyineri zable unsaturated monomer having two or more polyrnerizahie unsaturated sroups per molecule can be suitably selected according to the desired degree pi crossllnki.ng of the core copolymer i) the amount of the po lyruerizable unsaturated monomer having two or more polyinerizahie unsaturated aroups per molecule is preferably in a range of about 0.1 to 30 mass%, more preferably about 0.5 to 10 mass%, and even more preferably about 1 to 7 mass%, based on the total mass of the po.Iymerizable unsaturated monomer having two or more polymenizable unsaturated groups per molecule and the polymerizable unsaturated monomer having one polymerizable is unsaturated group per molecule, To suppress metl.nc mottling of the resulting coating film, the polymerizable unsaturated monomer having two or more polymeri zah.le unsaturated groups per molecule is preferahi.y an amide'containing monomer, such as methylene his (meth)acrylandde, ethylene his (math) acrylamide, etc. The amount of amide-containing monomer, when used, is preferably about 0.1. to 25 mass%, more preferably about 0.5 to B niass%, and even more preferably about 1 to 4 mass%, based on the toter maSS oJ the polymerizable unsaturated monomer having two or more polymerizable unsaturated groups per molecule and the unsaturated monomer having one polymerizable unsaturated group per molecule.
The polynterizable unsaturated monomer having one polymerizable unsaturated group per molecule, which is used as a monomer for the core copotymer (I), is a polynerizable unsaturated monomer that can he copolynierized with a polym.eri.zahle unsaturaued monomer having two or more polyruerizable unsaturated roups per molecule.
Examples of the polynerizabl.e unsaturated monomer having one pol.vmerizahle. unsaturated group per molecule include monomers (I) to xi) and monomers (xiii) to (xvii), which are polymerizable unsaturated monomers other than the polymer izable unsaturated monomers having two or more polyme.rizahle unsaturated groups per molecule, among the polymerizable unsaturated monomers listed as (m-2) component and (m-3) in the explanation of the copo.lynter Such monomers can be used singly, or in a combination of two or more according to the required properties of the core shell-type water-dispersible hydroxy- containing acrylic resin (Al'' ) --The hydroxy-cont.aining polymerizable unsaturated monomer used as a monomer for the shell copolymer (II) introduces a hydroxy group that can crossnnk with a currng agent (B) into a water-dispersible acrylic resin, and thereby functions to enhance the water resistance c.f the coating film and enhance the stability of-the water-dispersible acrylic resin in an aqueous medium. Examples of hydroxy--containinci polymerizable unsaturated monomers include monoesterified products of (rneth)acrylicac7d with a dihydric alcohol containing 2 to B carbon atoms, such as 2-hydroxyethyl (math) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth)acrylate, 4---hydroxybutyl (meth) acrylate, etc.; caprolactone---modif:Led products of the mc-noesterified product.s of (meth)acrylic acid with a dihydric alcohol containing 2 to B cat-*bon atoms; N-hydroxyuethyl. (meth)acrylamide; allyl alcohol; (meth) acrylate having a poiyoxyethylene chain with a terminal hydroxy group; etc. Such monomers can be used singly, or in a combination of two or more. Examples of monomers preferably used as the hydroxy-containing polwnerizable unsaturated monomer include 2-thydroxyethyl (meth) acrylate, 2hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (math) acrylate, etc. To provide a core-shell-type water-dispersible hydroxy-containing poltymerizable unsaturated acrylic resin with excellent stability in an aqueous medium and provide the coating film with excellent water resistance, the amount of hydroxy-containing polviaerizable unsaturated monomer is preferably about 1 to 40 mass%, more preferably ahci.t 4 to 25 mass%, and even more referahly about 7 to 19 mass%, based on the total. mass of the monomers constituting the shall copolmer (El) The hydrophobic polmierizable unsaturated monomer used as a moncner for the shell copolymer (11) is a polymerizable unsaturated monomer containing a.i i.near, branched or cyclic saturated or unsaturated hydrocarbon group containing 6 or more, more preferably 6 to.18 carbon atoms, excluding mononers contaIning a hydroph:ili.c group, such as hydroxy--containing polmierizabte unsaturated monomers. Examples of hydrophobic polymerizabie unsaturated monomers include alicyl or cycloalkyl (math) acrylates, such as n-hexyl (math) acryi.ate, octyl (math) acrylate, 2-ethylhexyl (math) acrylate, nonyl (math) acrylate, tr idecyl (math) acrylate, lauryl (math) acrylate, stearyl (math) acrylate, isostearyl (math) acrylate, cyclohexyl (math) acrylate, methylcyclohexyl (math) acrylate, tert--butylcyclohexy]. (math) acrylate, cyclododecyl. (math) acryl.ate, tricyciodecanyl (math) acrylete, etc..; isoborni.--containing polymerizabie unsaturated compounds, such as isobornyl (math) ac,.rylate, etc..; adamantyl-containing polymer.izahi.e unsaturated compounds, such as adamantyl (meth)acrylate, etc.; and aromatic ring-containing polymerizable unsaturated monomers.
such as benzyl (math) acrylate, styrene, crmethylstyrene, vinyltoluene, etc. Such monomers can be used singly, or in a combination of two or more.
To enhance 001 of the resulting coating film, the hydrophobic polymerizable unsaturated monomer is preferably a pol.ymerizah].e unsaturated monomer having an alkyl group containing 6 to 18 carbon atoms and/or a polymerizabl.e unsaturated monomer having an aromatic ring. Styrene is particularly preferable.
To provide a core--shell--type water-dispersible hydroxy containinq acrylic resin with excellent stability in an ac-ueous J meoaum. and provide the coating fitm with excellent water -..4 G-resistance, the ar.nourtt of hydrophobic polymerizable unsaturated monomer i.s preferably about: 5 to 50 mass%, snore preferably about 7 to 40 mass%, and even more preferably about 9 to 30 mass%, based cm the total. mass of the monomers constituting the shell copoIrer (II) The otfier polymerizabie unsaturated monomer(s) used as a monomer for the shell copolymer (it) are polymerizable unsaturated monomers other than hydroxycontaininq polymerizabie unsaturated monomers and hydrophobic polymer! zahie uns;.turated 1.0 monomers. Exples of such monomers include alkyl or cycloalkyl (meth)acryiates, such as methyl. (meth)acryiate, ethyl (meth) acrylate, n-propyl ( th) acrylate, iso--propyl (math) acrylate, n--hutyl (meth) acryla.te iso--hutyl. (meth) a:.ry].at.e, terthuty.i. (math) acrylate, etc..; and carboxy-containing 1.5 polymerizable urisat:urated monomers, etc. Such monomers can be used singly, a cosrx)ination of two or more. Specific examples of carboxy--containing olymerizat1e unsaturated monomers are the sane as mentioned above as examples of a monomer for the core copolymer (I) Acrvlio acid and/or methacryli acid are particularly preferable as a carboxy-containing polymerizable unsaturated monomer. By using a carboxy-containi.nr po.i.ymerizahle unsaturated monomer as other pol'riz&ble unsaturated monomer(s), the resulting core-shell te water-dispersible hydroxy-containing acrylic resin (Al'') becomes stable in an aqueous medium.
To provide a core-shell--type water-dispersible hydroxy-containing acrylic resin (Al'') with excellent stability in an aqueous medium and provide the coating film with excellent water reistance, the amount of carboxy-contalning polwnerizable unsaturated monomer is preferably about 1 to 30 mass%, more preferably about 5 to 25 mass%, and even more preferably about to 19 taess%, based on the total mass of the mono-mere constituting the shell copolymer (II) To enhance the luster of the resulting coating film, it is preferable not to use polrnerizahle unsaturated monomers having two or more polyme.rizahle unsaturated groups per molecule as the other polymerizable unsaturated monomers for constitutina the shell copolymer (II), thus forming an uncrossiinked copolyme.r 1Ii To enhance the appearance of the resulting coating fUr, the ratio of the copolymer (1) to the copolymer (II) in the core shell--type water--dispersible hyd.roxy-contain.tng acrylic resin (Al' ) is preferably n the range of about 5/95 to 95/5, more n.referahi.y 1.0/90 to 90/10, further preferably about 50/50 to 85/15, and particularly preferably about 65/35 to 80/20, on a solid-s basis.
To crovide the coating film with excellent water resistance, etc, the core-shell--type water-dispersible hydroxy-containing acrylic resin (Al' 2) preferably has a hydroxy value or about 1. to 70 mg K0h/g, more preterabiy aoout2 to 50 mg K0MTh, and even more preferably about 5 to 30 mg K0H/q.
To provide the coating composition with excellent storaae stability and provide the coating film with excellent etc. * the core-shell-type water-dispersible hydroxy-containing acrylic resin (Al.' preferably has an acid value oil about 5 to about 30 mg KOH/g, more preferably about S to about. mg KCH/g, and even more preferably about 10 to about mg K(H-1/g.
The core-shell-type water-dispersible hydroxy-containing acrylic resin (Al'') can be prepared by a process comprising: subjecting to emulsion polymerization a monomer mixture of about 0.1 to 30 mass% of a polymerizable unsaturated monomer having two or more nolymerizahie unsaturated groups per molecule, and about 70 to 999 mass% of a olymerizahle unsaturated monomer having one polvnerizable unsaturated group per molecule to form an emulsion of a core copolymer (I); adding to tins emuision a monomer rixtur of about I to 40 mass% of a hydroxy'-containing polymerizable unsat rated monomer, about 5 to mas s% of a hydrophobic polymerizable unsaturated monomer, and about 10 to 94 mass% of other nolaerizab1e unsaturated monomer(s) and further performing emu].s ion pol.vrnenzata.on to form a shell copolymer (11) The emulsion polymerization for preparing an emulsion of the c:ore oopo.iymer (I) can be car:ried out according to known methods. For exampi, the emulsion can he prepared by subjecting the monomer mixture to emulsion polymerization using a polymerization initiato.. in the presence of a surtactant, For the above surfactant anionic surfactants and ron ionic su.rfactant.s are suitable. xampies of arucc surfactants include sodium salts and airimonium salts of alkylsultonic acids, alkylhenzenesulfonic acids, alkyiphosphoric acids, etc. Examples of nonionic surfactants include polyoxyethyiene oi.eyl ether, pol.yoxyethyiene stearyl ether, olyoxvethy.i.ene lauryl ether, polyoxyethylene tridecyl ether, 1.5 polyoxyethyie.ne phenyl ether, polyoxyethylene nonvlphenyl ether, po.Lyoxyethvle.ne octylphe.nyl ether, polyoxyethylene monolaurate, polyoxye.thylene raonosLearate, polvoxyethylene moriooleate, sorbitan monolaur-ate, sorbitan monostearate, sorbitan trioleate, poiyoxyethylenesorhitan monolaurate, etc. Other examples of usable surf actants include polyoxyalkylene-coritaining anionic surfactants that have an anionic roup, a pol.yoxyalkylene groLp, such as a polyoxyethylene group, poi.yoxyDronylene group, per molecule; and reactive anionic surfact nts that. have Cr: anionic qroup and a radically Dolymerizabl.e unsaturated group per molecule. Among these, reactive anionic surfactants are preferable.
Examples of reactive anionic surfactants include sodium salts of sulfonic acid compounds having a radically poi.ymerizable unsaturated group, such as allyl, methallyl, 30. uneth) acryloyl, propenyl, hutenyl. or the like; axmr.onium salt of such sulfonic acid compounds. etc. Among these, annonium salts c..uifcnic acid compounds having a radically polymerizable unsaturated group are preferable in view of the excellent water resistance of the resulting coating film. Examples of copxnerciafly available nunonium salts of such sulfonic acid compounus include "LATEt4UL S-1BCA" (tradename of Kao Corporation) Pnong the ammonium salts of sulfonic acid compounds having a radically polymeri zabi.e unsaturated group, ammoniuni salts of sulfonic acid compounds having a radically polymeri.zahle unsaturated group and a polyoxyalkylene group are particularly preferahle Commercially available ammonium salts of sulfonic acid compounds having a radically polymerizable unsaturated group and a poiyoxyallcylene group include "Aqualon EH-l0" (tradename, Dai-Ichi Kogyo Selyaku Co., Ltd.), "LATEMUL P0---104" (tradenaine, Kao Corporation), "Adeknaria Soap SR---l.025" (tradename of ADEKA Co, LtW) etc. The amount. or sartactant. is preferably about 0l to 15 mass%, more preferably about 05 to 10 mass%, and even more preferably about I to 5 mass%, based on the total mass of. the monomers used.
Examples of nolvmerization initiators include organic peroxides such as benzoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, cumene hydroperoxide. tert-hutyl peroxide, di-tert-amyl. peroxide, tert-butylperoxy---2--ethyl.hexanoate, tert-butyl peroxylaurate, tert-butyl peroxyisopropyicarhonate, tert-hutyl peroxyacetate, diisooropylbenzene hydroperoxida, eLc.; azo compounds such as azobisxsooutyronitri.ie, azohis (2, 4-damethyivaieronitri.le), azobis (2-rethylpropionenitrile), azobis(2-methylbutyronitrile) 4,4' -azohis (4-cyanobutanoic acid), dimethyl azobis (2-methyl propionate), azobis[2-methyl-N-(2-hydroxyethyl) -ropionamideJ, azobi.s [2-metihvl-N-[2-(1-hydroxy butyl) J-oropionamide], etc: persulfates such as potassium persulfate, ammonium persulfate, sodium persulfate, etc; etc. Such polw1erization initiators can be used singly, or in a combination of two or more Redox initiators prepared:lJy cornbrnirg a poiymer.izat:wn initiator as mentioned above with a reducing agent such as sugar, sodium formaldehyde suifoxylate, iron comolex, ec. iray also be used.
The amount of polymerization initiator is generally preferably about 0.1. to 5 mass%, and more preferably about 0.2 to 3 mass%, based on the total mass of. -all of the monomers used.
Th.e method of addino tite polymerization initiator i.s not panicular.ty nmited, aria canoe suitably selected accotmng o the kind and amount of polymerization Initiator used. For exanniLe, the polymerization initiator may he incorporated into a monomer mixture. or an aqueous medium beforehand, or may be added -dropwise or all at once at the time of polymerization.
The core-she! i-type water-dispersible hydroxy-containing acrylic resin (As''; can he obtained by adaing to the above-obtained emulsion of the core copolymer (I) a monomer mixture of a hydroxy-containing polymerizable unsaturated monomer, a hydrophobic polymerizable unsaturated monomer, and other pdlyrnerizahl.e unsaturated monomer(s), and further performing polymerization to form a shell copolnuer (II) The monomer mixture for forming the shell copolymar (Ii) may optionally contain other components such as polymerization initiators as mentioned above, chain transfer agents, reducing agents, and suri:actants, etc. The monomer mixture is preferably added dropwi.se as a monomer emulsion obtained by dispersing the monomer mixture into an aqueous mediwn, although it may he added dropwisc as is. In this case, the particle size of the monomer emulsion i not particularly -limited.
The method for pol.ymerizing -the monomer mixture for forming the shell copolymer (II) comprises, for examele, adding the monomer mixture or. emulsion thereof dropwise to the emulsion of the core copolymer CI) all at once or gradually, and heating to a suitable temnerarure while stirring.
The core-shell-type water-disoersihle hyd.toxv- containing acrylic, resin (M.'' ) thus obtained has a multiple-layer structure comprising a core copolymer (1) of...* a monomer mixture of a polynerizable unsaturated monomer having two or more polymerizab!.e unsaturated qroup per molecule and a polacrizable unsaturated monomer having one polymerizable 1.-unsaturated group per molecule, and a shell copolymer (11) of a monomer mixture of a hydroxy---containinq polymerizable unsaturated monomer, a hydrophobic polymerizable unsaturated monomer, and other polymerizable unsaturated monomer(s) The core-shell--type waterdispersible hydroxy-containing acrylic resin (Al'') thus obtained usually has a mean particle size of about 10 to 1,000 cm, and particularly about 20 to 500 nm. In this specification, the mean particle size. of the core-shell-type water-dispersible hydroxy--containing acrylic resin (Al'') refers to a value obtained by measurement at 20 C: using a submicron par tide size distribution analyzer after dilution with deionized water according to a usual method. For example, a COULTEP. 144" (tradename, Beckman Coulter, Inc) can be utsed as the subm.i.crcn particle size distribution analyzer.
To amnrove the mechanical stability of the particles of the core-shell--type water-dispersible hydroxy-coataining acrylic resin (Al!'), acid groups such as carhoxy groups of the water--dispersible acrylic resin are preferably neutralized with a neutralizing agent. The neutralizing agent is not particularly limited, as long as it can neutralize acid groups. Examples of such neutralizing agents include sodium hydroxide, potassium hydroxide. trimethylamine, 2-(dlmethylamino) ethanol, 2-amino--2-- methyl-i-propanc.L, trietbylandne, aqueous ammonia, etc. Such a-neutralizing agent is preferably used in an amount such that the pH of the aqueous dispersion of the water-dispersible acrylic resin after neutralization is about 6 5 to about: 50.
Further, it is also preferable that the water-- dispersible hydroxy-containing acrylic resin (Al') have a core--shell structure with a cross.linked core in terms of improving stability of the resulting water-dispersible hydroxy-containing acrylic resin (Al') in an aqueous medium.
More preferably, to enhance the smoothness, 001, luster and water resistance of the resulting coating film, the water--dispersible hydroxy-containing ac:c:yL.c resin (Al.' 3 is preferahl.y a core-shell-type water-dispersible hydroxy-containing acrylic-resin (Al' --i) which has a core-she11 structure having, as the core, copolymer (1:: containing, as monomer compor.ents. 3.1 to 30 5585% of a pcslym.erzan1e unsaturated monomer havinu two or more polymerisabie unsaturated grouns per molecule and a 70 to 99.9 mass% or a polymenzao.ic unsaturated monomer flaying one polymerizable unsaturated group per molecule, based on the total iriass of the monomer components constituting the core, The core---sheli-'tyoe water dispersible hydroxy-containing acrylic resin (Ai'-'U contains 5 to It) vasst of a hycfraphok ic polymunz £ unsaturated monomer b-) 0.1 to 25 mass at nydroxy'-containing polymeri.zable unsaturated monomer (b-2) * 0.1 to 20 mass% of carhoxy-containing polymerizable unsaturated monomer. (h-3) and o to 94.8 mass% of polymerizable unsaturated monomer (b-4) other than the polymensabie unsaturated. monomers (b--i) to (b3) based on the total mass of the monomer cononents constituting the core and the shell.
Examples of the polyinerizable unsaturated mononers having two or more polymerizable unsaturated groups per molecule used as a monomer for the core copolyrner (I) of the core-shell--type water--dispersible hydroxy--containing acrylic resi.n (Al! ---1) are the same as those listed above. Such monomers can be used singly, or in a combination of two or more.
?urther, the amount ot the pclymerizable unsaturated monomer having two or more polymerizab i.e unsaturated groups per molecule is the same as that specified above.
The polymerizahie unsaturated monomer having one po.Iymerizable unsaturated group per molecule, which:1.5 used as a monomer for the core copolyner (I) of the core-shell--type water---di.s;ersibl.e hydroxy-contein.inq acrylic resin (Al' -1) * is a polyinerizable unsaturated monomer that can be copolynerized with a po.lymeri.zahie unsaturated monomer having two or more polymerizable unsaturated groups per molecule.
Specific examples of the polyinerizable unsaturated monomer having one po.i.ymerizahi.e unsaturated group per molecule include alkyl or cycloalkyl (meth) acrylates such as methyl (meth)acrvlate, ethyl (meth)acrylate, n-propyi (meth.) acryl.ate, isopropyl (meth) acrylate6 nbutvl (math) acrylate, Isobutyl (meth) .acry.Late, tert-hutvl (meth) acrylate, n-hexyl.
(meth) acrylate, noctyi (meth) acryla:e, 2 ethy.thexyi meth) acrylate, nonyl (math) acrylate, tridecyl (math) acrylate, lauryl (math) acrylate, stearyl (meth) acrylate, "isostearyl Pcryiate (tradename, Osaka Organic Chenical Industry, Ltd. ) cyelohexvl (tueth) acryl.ate, methyicycl ohexl (math) acrylate, t-butvlcyclohaxyl (neth) acrylate, cycic&decyl (metli) acrylate, and tricyclocIecanyl. (math) acrylate; isobornyl-containing polyseri sable unsaturated monomers such as isobornyl (math) acrylate; aoamant.yl--containing polymerizable unsaturatect monomers such as adamantyl (math) acrylate; tricyclodecenyF containing poJ.yme.r:Lzabie unsaturated monomers such. as tr.icyc.todeceny.l. (meth)acrv.late; aromatic ring-containing polymerizable unsaturated monomers sucii as henzyl (me:Lh) acrylate, styrene, a-metny..styrene and vi.ny.lto.].uene;-a.Uoxysilyi-containing polymerizahie unsaturated monomers such as vinyltrimethoxysilane, vinyitriethoxysilane, vinyitris (2 2.0 methoxyathoxy) silane, y-(math) acrvioyloxypropyitriinethoxysiiane and y (math) acryIoyloxypropyltriethoxysiiane; perfiuoroalkyi (math) acrylates such as perfluorobutviethyl (moth) acrylate and pert.Luorooctylethyl (meth)acrylate; flun rinated al.kyl--containinct polymerizable unsaturated monomers such as fluoroolefinsF polsrnerizable unsaturated monomers having photopolynerizabl.e functional groups such as a maleimide group; vinyl compounds such as N-vinylpyrrolidone, ethylene, butadiene, chioroprene, vinyl propionate and vinyl acetate; hydroxy--containing polnerizabie unsaturated monomers such as monoesteri..tied products of (meth)acryli.c acid with a dihydric alcohol containing 2 to B carbon atoms such as 2-hydroxyethy1 (math) acrylate, 2-hydroxypropyl (math) acrylate, 3--hydroxypropyl (math) acrylate and 4 -hydroxybutyl (math) acrylate, caproiactone-slodl::Led products of the inonoesterified products? N-hydroxymethyl (math) acrylaznide, allyJ. alcohol, and (math) acryi.ates having hydroxy-terminated polyoxyethylene chains; carboxy-containing polymerizabie unsaturated monomers such as (meth) acrylic acid, maleic acid, crotonic acid and ft-carboxyethyi. acrylate; nitrogen-cc:.ntaining po.iymerizable unsaturated monomers such as (math) acryionitr.ile, (meth) acrylamlde, N,N --dimethylaiminoethv.i (meth) acrylate, N,N---diethylaminoethyl (math) acrylate, N, N-dimethylaminopropyl (meth)ac.rylamide and adducts of glycidyl (met.h)acrylate with amine compowids; epoxy-containing polymerizable unsaturated monomers such as glycidyl (meth) acrylate, --methylglycidyl (math) ac.rylate, 3, 4-epoxycyclohexylmethyl (math) acrylate, 3,4-epoxycyclohexyi.ethyl (math) acryi.ate, 3, 4-epoxycyclohexylpropyl.
(meth) acrylate and allyl glycidyl ether; and (zneth) acrylates having aikoxy-ternd nat S poj.yoxyethylene chains. TI:ese monomers 1.5 can be used singly, or in a combination of two or more, depending on the performance required for the core-shell type water--dispersih.i e hydroxyl-containing acrylic re sin (Al' -I) -For the polymerizable unsaturated monomer having one polymerizable unsaturated group per molecule,itis preferable to use, at least partially, polynerizable unsaturated monomer having a Ci or 02 alkyi group.
Examples of the polymerizable unsaturated monomer having a Cl. or 02 alky.1 group include methyl acrylate, methyl methacrylate, ethyl acrylate and ethyl methacrylate. These monomers can be used singly, or in a combination of two or more.
When the polwnerizahle unsaturated monomer having one polymerizable unsaturated group per molecule includes the polymerizable unsaturated monomer having a Ci or 02 alkyl the amount of the above-mentioned poi.ymeri sable unsaturated monomer having a Cl or C2 alkyl group is preferably about 20 to 99.9 mass%, more prefferably about 30 to 99.5 mass%, and even more preferably about 40 to 99 mass%, based -on the total mass of the oolymerizable unsaturated monomer havinq one polvmerizable unsaturated group per molecule and the poi.ymeri.zahle unsaturated monomer having two or more polymerizable unsaturated groups per molecule, in tems off.improvi rg the smoothness, 001 and luster of: the resulting coating film.
The core-shell type wate.r-di.spe.rsibi.e tivdroxyl-containing acrylic resin (Al' --1) usually has a mean particle size of about 10 to 1,000 nut, and oarti.cularly about 20 to 500 urn.
In this specification, the mean particle size of the bore-shell-type water-dispersible hydroxyl-containing acrylic resin (Al'---l) refers to a value obtained by measurement at 20°C using a dynamic liqht-scstterinq oarticl.e size distribution analyzer after dilution with deionized water according to a usual method. For example, an 1N5 Suhisicron Particle Size Analyzer" (tradename of}Sec}anan Coulter, IncJ can be used as the dynamic ngnt-scattenng particIE.. size distribution analyzar.
To improve the mechanical stability of the particles of the core-shell type water-dispersible hydroxyl.-contai.ning acrylic resin (Al' -1), acidic groups such as carboxyl groups of the water-dispersible acrylic resin are preferably neutralized with a neutralizing agent. Any neutralizing agent that can neutralize acidic groups car: be used. Example-s of the neutralizing agent include sodium hydroxide, potassium hydroxide, triruethyl.ami.ne, 2-(dimethy].ami.no) ethanol, 2-am:in.o--2--methylil-propanci, triethylamine, aqueous arrmonia, etc. The neutralizing agent is preferably used in an amount such that the pH of an 23 aqueous dispersion of the neutralized water--dispersible acrylic resin is about ES to -about 90.
More preferably, to 001, luster and water resistance of the resulting coating film, the core-shell-type water-dispersih].e hydroxy-contain ing acrylic resin (Al' -1) Is preferably a core-shell-type water-dispersible hydroxy-containing acrylic resin (U' -2), which hasa core-shell structure having, as the core, copolymer (1) containing, as monomer components, 0l to 30 mass% of a poiymerizahle unsaturated monomer having two or more polymerizable unsaturated groups per molecule and a 70 t.o 99.9 mass% of a polynerizable unsaturated monomer: having one poIymer.zabi.e unsaturated group per molecule and, as the shell, copolaer (II) containing, as monomer components, S to 60 mass% of a hydrophobic poiymerizab±e unsaturated monomer (h--i), On to 50 mass% of hydroxy--containing poi.ytner.izahl.e unsaturated monomer (b-2) * Onto 50 mass% of ca.rboxv--containinq polyinerizable unsaturated monomer (b-3), and 0 to 94J waass% of poiymeriable unsaturated monomer (b-4) other than the polymerizable unsaturated monomers (h-i) to (h-3) The ratio of copolymer (I) to copolymer (II) in solids content by mass is in a range of from copolymer (1)/copolymer (II) = 5/95 to 95/5. To erthance the smoothness, DOt, luster and water resistance of the resulting coating film, the ratio of copolymer (I) to copolyner (ii) in solids content by mass is preferably about 50/50 to 85/i5 more r-refe-rahly about 65/35 to 80/20.
Althoucth the amount of the polyrnerizable unsaturated monomer having two or more polymerizable unsaturated groups per molecule in the core shell--type water---dispers.ih].e hydroxy--containing acrylic resin (Al' 2) can be suitably selected according to the desired degree of crosslinkincr of the core copolymer (I), the amount i.s preferably about 0]. to 30 mass%, more preferably about 0.5 to 10 mass%, and even more preferably about]. to 7 mass%, based on the total mass of the polymerizabie unsaturated monomer having two or more polymerizable unsaturated groups per molecule and the unsaturated monomer having one polymeri.zabl.e unsaturated group per molecule.
in the core-shell--type water-dispersible hydroxyl-containing acrylic resin (Al' -2) the amounts of hydrophobic polyrnerizable unsaturated monomer (b-i), hydroxy-containina polymeri sable unsaturated monomer (h-2) , carhoy-containing olymerizab1e unsaturated monomer:(b3) and -poi.ymerizahie unsaturated ronomer(b-4) other than the polymerizabie unsaturated monomers (b-I) to (b---3) in the shell preferabi.y tall within the following ranges in terms of ensuring stability in an aqueous medium, and in terms of improving the smoothness, 001, luster and water resistance of the resulting coating film. The following ranges are based on the total mass of the monomers constituting the shell.
Hydrophobic polymerizable unsaturated monomer (b-4) 5 to 80 mass%, preferably 7 to 70 macsi. more preferably 8 to 65 irass%; Iiydroxy---containing pa]. ymerizahl.e unsaturated monomer (h-2); 0.1. to 50 mass%, preferably 4 to 25 mass%, more preferah].y 7 to 19 macsi; Carboxy-containing polaerizabie unsaturated monomer (b-3): OJ. to 50 macsi, preferably 5 to 25 mass more preferably 7 to 19 massi; Polyn.e.rizah.ie unsaturated monomer (b-4) other than polymorizable unsaturated monomers (bl) to (b3): 0 to 948 1Ec359%, preferably 10 to 84 macsi, more preferably 15 to 78 macsi.
To enhance the smoothness [I and luster of the resulting coating film, it is preferable not to use the pol.ymerizah.Ie unsaturated monomers having two or more polyncarizable unsaturated groups per molecule as the other polyrnerizanle unsaturated monomer (s) for the shell copoiymex (II), thus fanning an uncrosslinked copolymer (ii) The core-shell---tvpe waterdispersihle hydroxy containing acrylic resin (A1 -2) can he prepared by a process coxnpri.s.inq subjecting to emulsion polymerization a monomer mixture of about 01 to about 30 mass% of a polymerizahl.e unsaturated monomer having two or more polymerizable unsaturated groups per molecule, and anout 70 no about. 999 macsi at a polymerizable unsaturated monomer having one polymerizahie unsaturated group per molecule to form an emulsion of a core copolymer (I); addin.g to this emulsion a monomer mixture of 5 to 80 mass% of a hydrophobic polymerizable unsaturated monomer (b 1.) , 0.1 to 50 macsi of. a hydroxycoritai.ni.ng oolvmeriza.ble unsaturated monomer (b-2), 0.1 to 50 macsi of acarboxy--containing polymerizable unsaturated monomer (b-3, arid about 0 to 94 mass% of polytr:erizahl.e unsaturiited monomer (s) (h-4 other than polymerizabie unsaturated monomers (b1) to (b3), and further performing emulsion polymerization to form a shell copolymer. (Ii) The emulsion polymerization for preparing an emulsion of the core copolymer (1) can be carried out according to known methods. For example, the emulsion can be prepared by subjecting the monomer mixtu±e to emulsion polymerization in the presence of a surfactant using a polymerization initiator.
The surtactant and the polymerization initiator may he selected from the above-mentioned examples. The anunLs of the surfactant and the polymerization initiator can also be deterirdned according to the above-mentioned range.
The core--shell--type water-dispesible hydroxy-containing acrylic resin (Al' 2) can he obtained by adding to the above-obtained emulsion of-the core copolymer (I) a monomer mixture of a hydrophobic polymer i.za.h.I.e unsaturated monomer (h-i), a hydroxy-containirig nolymerizable unsaturated monomer (b-2), a carhoxy---containthq poiwuerizahi.e unsaturated monomer (h--I) and a polymerizable unsaturated monomer (s) (b-4) other than polymerizable unsaturated monomers (b-I) to (h-3}, and further performing polymerization to form a shell copoi.ymer CII) -The monomer mixture for faming the shell copoltar (II) may optionally contain other components such as moi.ymerizati.on initiators as mentioned above, chain transfer agents, reducing agents, and surfactants, etc. The monomer mixture is preferably added dropwise as a monomer emulsion -obtained by dispersing the monomer mixture into an aqueous medithm, although it may be added dropwise as is. in this case, the particle size of the monomer emulsion is not particularly limited.
The method for polymeri.zing the monomer mixture for forming the shell copolymor (Ii) comprises, for exampre, adding the monomer mixture or emulsion thereof dropw.ise to the emulsion of the core cop-olymer (I) all at once or gradually, and heating to a sui.ttahi.e temoerature while stir-ring.
Che core--shell-type water--dispersible hydroxy- containing acrylic resin (Al' 2) thus obtained has a multiple-layer structure comprising a core copolymer (I) of a monomer mixture of a po.lytnerizahi e unsaturated monomer having two or more polvinerizable unsaturated gro ups per molecule and a polyntenzaDle unsaturated monomer having one polnerizable unsaturated group per molecule, and a shell copolymer (II) of a monomer mixture of a hydrophobic polvmer.izahi.e unsaturated monomer (h-i.) * a nydroxy-cuntai.nirig poiymer.zabi.e unsaturated monomer (b-2), a carboxy-containing oolvmerizable unsaturated monomer (5-3) and a polymer! zahie unsaturated monomer(s) (b-4) other than polvmerizahle unsaturated monomers (b-I) to (b-3) -PJ i v].w2sturPcs..n(A2) In the aqueous coating composition of the present invention, use of-a hydroxy-contai.n.i.ng polyester resin (A2) as the film--formi.ng resin (A) improves the performance of the resulting coating film in terms of smoothness, DOI water resistance and the like.
The hydroxy--containing polyester resin (A2) can usually be produced by an esterificat ion reaction or transesterification reaction of an acid component with an alcohol component.
rhe acid component may ne a corupouna that 15 conventionally used as an acid component for producing a polyester resin. Examples of such acid components include aliphatic polybasic acids, alicyclic poloasic acids, aromatic polybasic acids, etc Generally, aliphatic noi.ybasi.c acids include aliphatic conrcourids having at least two carhoxy groups per molecule; anhydrides of such aliphatic compounds; and esters of such al ipliatic compounds. Examples of aliphatic polyhasic acids include succinic acid, glutaric acid, adipic acid, pimelic acid, superic acid, azelaic ac:id, sebac:i.c acid, undecanedioic;acid, dodecanedioic acid, brassylic acid, octadecanedi.oic acid, citric acid, butane tetracarboxylic acid, and like aliphatic polycarboxylic acids; ar-hydrides of such a i.iphat ic polycarboxylic acids; esters of such aliphatic polycarboxylic acids with about C1-C4 lower alkyis; etc. Such a.liphatic polybasic acids can he used singly, or in a cordination of two or mure.
in terms of the smoothness, DOT etc. of the resulting coating film, it is particularly preferable to use adipic acid and/or adipic anhydride as an aliphatic polybasic acid.
Generally, alicyclic polybasic acids include compounds having at iet one ali.cyclic structure and at least two carboxy groups per molecule; acid anhydrides of such compounds; and esters of such corrpounds. The al.icyciic structure is typically a 4-6 membered ring structure, Examples of alicyclic polybasic acids include 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1, 4---cyciohexanedicarhoxy.lic acid, 1-cyciohexene-1, 2-dicarboxylic acid, 3-methyl-i, 2- cyclohexanedicarhoxyl.ic acid, 4-methyl--i, 2-cyclohexanedicarboxylic acid, 1,2, 4-cyciohexanetricarboxylic acid, 1,3, 5---cyclohexanetric2rhoxylic acid, and like alicycuc polycarboxylic acids; anhydrides of such alicyclic polycarboxylic acids; esters of such alicyclic polycarboxylic acids with about Cl-C4 lower aikyis; etc. Such auicyci.ic polybasic acids can be used singly, or in a combination of two or more.
In terms 0± thernoothnes, XL1 etc. of the resulting coating film? preferable alicyclic polybasic acids include 1,2-cyclohexanethcarvoxylic acm, 1, 2-cyc±ohexanedicarboxytic anhydride, 1, 3-cyclohexanedicarhoxyl ic acid, 1,4-cyclohexanedicarboxylic acid, 4-cyclohexene-1,2--dicarboxylic acid, and 4--cvclohexene--l,2-dicarboxylic anhydride imong these, it is particularly preferable to use 1, 2-cyclohexanedicathoxylic acid and/or 1, 2--cyclohexanedicarhoxyii.c anhydride.
Generally, aromatic polyhasic acids include aromatic compounds having at least two carhoxy groups per molecule; anhydrides of such aromatic compounds; and esters of such arorratc compounds. Examples of aromatic polybasic acids inclt.ide $5 phthalic acid. isophthalic acid, terephthalic acid, -6l naphthalenedicarhoxylic acid, 4 4 -binhenyldicarboxylic acid9 trimellitic acid, pyromelJ itic acid, and like aromatic polycarboxyL.c acids; anhydrides of such aromatic polycarboxylic acids; esters of such aromati.c polycarhoxylic acids with about Cl to about 04 lower aikyls; etc. Such aromatic pblybasic acids can he used singly, or in a combination of two or more.
Preferable aromatic polybasic acids include phthalic acid, phthaii.c anhydride, iscphthalic acid, trimefliti.c acid, and trimellitic anhydride.
Acid components other than aliphatic polybasic acids, alicyclic polybasic acids, and aromatic polyhasic acids can also he usech Such other aci.d components are not limited, arid include, for example, coconut oil fatty acid, cottonseed cii fatty acid, nempseed o.l. fatty acid, rice bran oil tatty acia, fish oi.l fatty acid, tall oil fatty acid; soybean oil fatty acid, linseed oil fatty acid, tung oil fatty acid; rapeseed oil fatty acid, castor oil fatty acid, dehydrated castcu oil: fatty acid, safflower oil fatty acid, and like fatty acids; lauric acid, myristic acid, palmitic acid, steari.c. acid, oleic acid, lirtolic acid, .Linolenic acid, benzoic acid, o-tert-butyl bensoic acid, cyclohexanoic acid, i0---phenyloctadecanoic acid, and like monocarboxylic acids; and lactic acid, 3---hydroxybutanoic acid, 3-hydroxy-4-ethoxyberizoic acid, atri like hydroxycarboxylic acids.
Such acid components can he used singly, or in a combination of two or more Pclyhydric alcohols having at least. two hydroxy groups per molecule can be preferably used as the above--mentioned alcohol component. Examples of such polyhydric alcohols include ethylene glycol, propylene glycol, diethylene glycol, trimethylene glycol, tetraethylene glycol, triethylene glycol, dipropylene glycol., 1, 4-hutanecLtoi., 1, 3-butanediol, 2,3- butanediol, l,2-batanediol, 2-methyl--i, 3--propanediol, 3--methyl--- 1, 2-butanediol, 2-*-butyl---2--ethyl---l, 3-propanediol, I, 2-pentanediol, 1, 5-pentanediol, 1., 4---pentanedioi, 2, 4-pentanedioi, 2,3- dimethyitrimethylene glycol, tetramethylene glycol, 3-methyl-- 4, 3--pentanedi.ol, 3-methyl--l, 5--pentanediol, 2,2, 4--trimethyl.--l, 3---pentanec{iol, 1, 6-hexanediol, 1, 5-hexanediol, 1, 44iexanedioi, 2, 5--hexanediol, neonentyl glyc6i, 1, 4--cyclohexanedimethanol, tricyclodecanedimethanol, risopentyl yJycol hydroxypivalate ester, S hydrogenated bisphenol A, hydrogenated bisphenol F, dimethylol propionic acid, and like dihydric alcohols; polylactone thols obtained, by adding lactone compounds, such as e-caprolactone, to such d.ihydric alcohols; his (hydroxyethyi) Lerephthalate and like ester-dial -compounds; alkylene oxide adducts of bisphenol A, polyethylene givcols, polvpropylene glycols, polyhutylene glycols, and like polyether dial compounds; glycerol, trimethylolethane, trlrnethy1olpropane diglycerol, triclycerol, 1,2, 6--hexanetriol, pentaerythritol, dipentaerythritol, tris (2-hydroxvethyl) isocyanuric acid, sorbitol, marinitol, and like trihydric or higher polyhydric alcohols; poiylactone pol-joJ.
compounds obtained by add.in.iactone compounds, such as s--caprolactone, to such trihydric or higher polyhydric alcohols; and fatty acid esters of glycerol, etc. Alcohol conponent.s other than polyhyd.ric alcohols can also be used. Such other alcohol components are not limited, and include, for example, methanol, ethanoL propy] alcohol, butyl alcohol, stearyl alcohol1 2-phenoxvet.hanol, and like monohydric alcohols; alcohol compounds obtained by reacting, with acids, propylene oxide, hutylene oxide, "Cardura ElO" (tradename of HEXION Specialty Cheiracals; glycidyl ester of a synthetic highly branched saturated fatty acid), and like monoepoxy compounds; etc. The production method f or the hydroxy-containing polyester resin (A2) -is not limited, and may he performed by any usua.l method. For examnie, the hydroxy--containing polyester resin can be produced by heating the acid component and alcohol component in a nitrogen stream at about 150 to about 250'C for about 5 to 10 h-ours to thereby carry out an estérification reaction or transesterification reaction of the acid component with the alcohol comoonent-For the esterif:ca1::on reaction ortransesteri..fication reaction, the acid component and. alcohol component may be added to a reaction vessel at one time, or one or both of the components may be added in several portions Alternatively, a hydx:oxy--containing polyester resin may be. first synthesized and then reacted with an aci.d anhydri.de for hal f-esterification to thereby obtain a carboxy-and hydroxy-contatning polyester resin.
Further alternatively, a carhoxy-containinq polyester resin may be first synthesized, and the above-mentioned alcohol component may be added to obtain a hydroxycontai.ning polyester resin.
For promoting the esterification or transesterification reaction, known catalysts are usable, including, for example, dibutyltin oxide, antimony trioxide, zinc acetate, manganese acetate, cobalt acetate, calcium acetate, lead acetate5 tetrabutyl titanate, tetraisopropyl titanate, etc. The hydroxy--conta.]ning polyester resin (A2) can be modified with a fatty acid, manoepoxy compound, polyisooyanate compound, or the like, during or after the preparation of the resin.
xamples of the J-atty acid incnde coconut oil fatty acid, cottonseed oil fatty acid, hempseed oil fatty acid, rice bran oil fatty acid, fish oil fatty acid, tall oil fatty acid soybean oi.l fatty acid, fiaxseed oil fatty acid, tong oil. faLty acid, rapeseed oil fatty acid, castor oil. fatty acid, dehydrated castor Dii fatty acid, safflower cii fatty acid, etc. Preferable exampi.es of the monoepoxy compound include Cardura ElO" (tradename of HEXION Specialty Chemicals; glyoidyl ester of a synthetic highly branched saturated fatty acid) Examples of the polyisocyanate compound include lysine diisocyanate, hexarnethylene dilsocyanate, trimetthylhexane dii socyanate, and like aliphatic d±isocyanate compounds; hydrogenated xylylene dilsocyanate,. isophorone dilsocyanate, rnethyicyciohexane2, 4diisocyanate, methylcycl.ohexane2, 6-- dilsocyanate, 4,4 --methylene his (cyclohexylisocyanate) , 1, 3-isncyanatomethyi) cyciohexane, and like alicyclic diisocyanate compounds; tolylene diisocyanate, xylylene diisocyanate, thphenvlmethane diisocyanate, and like aromatic diisocyanate compounds; organic pn Lv.l.socyanates, such as.iysine tr.tisocyanate and like tn-or higher polisocyanates; adducts of such organic polyisocyanates with polyhydric alcohols, low--nolecular-weight oolyeste.r resins * water, and/or the lIke; cvcl.ooo.1.yraars Ce g isocyanurate), biuret adducts etc, of such organic polyisocyanates; etc. Such polyisocyanate compounds car.. be used singly, or in a combination of two or more.
tn the hyd.roxvconta±ning polyester resin (A2) to obtain a coating fun with excellent smoothness, WI and excellent water resistance, the proportion of. alicyclic polybasic acid in the acid cotonenbs used as starting materials is, based on the total amount of the acid components, preferably about 20 to 100 mol%, more preferably about 25 to 95 mcl%, and even more preferah.1.y about 30 to 50 molt. ]n particular, it is preferable to use, as an alicyclic polvbasic acid, 1,2-cyclohexanedicarboxylic acid and/or 1, 2-cyclohexanedi.carboxylic anhydride, i.n tens of providing a coating film with excellent smoothness, 1)01 etc. of the resulting coating film.
The hydroxy-containing polyester resin (A2) preferahl.y has a hydroxv value of about. 1. to 200 rug KOH/g, more preferably about 2 La 180 rag KOH/g, and even more preferably about 5 -to 170 rag KOH/g. When the hydroxy-containinc polyester resin (7) also has a carboxy group, the acid value of the resin is preferably about 5 to 150 rnq K0H/g more preferably about 10 to 100 rag K0H/q, end even more preferably abbut 1.5 to 80 mg KOF1/g. The hydroxy-containing polyester resin (A2) preferably has a number average molecular weight of about 500 to about. 50,000, more preferably about 1,000 to about 30,000, and even more preferably about 1,200 to about 10,000.
The above hydroxy-containing polyester resin (A2) can he neutralized using a basic compound. Examples of basic comnounds include hydroxides of alkali, metals or alkaline earth metals such as sodium htdroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide * and barium hydroxide; ammonia; primary monoamines such as ethylamine, propylamine, hutylamine, bE?nzyiamlfle, moncethanolami.ne, 2, 2-di.methyl---3-amino-1.-p.ropano.].
2--aminopropanol, 2nino2-methyL-ipropanol, and ama.nopropanol.; secondary monoanunes such as diethylamine, diethanolamine, di-n-propanolamine, di.--iso---propanoiamine, methylethanolamine, and N-ethylethanolaxnine; tertiary monoaird.nes sucn as dimethyl.ethanoi.ami.ne, trimethylamine, t.nethylam.ine, triisopropylaniine, metnyrdiethanolamine, and 2- (dimethylamino) ethanol; polyamines such as diethylenetriamine, hydroxyethylaminoethyiantine, ethylaminoethylaxaine, and methylaminopropylarnine; etc. Such hasi.c compounds can he used singly, or in a cothbination ci two ormore. It is preferable to use a water-soluble basic compound..
rrhe amount of the hydroxyconLaining polyester resin A2) in the aqueous coating composition of the present invention is generally 2 to 70 mass%, preferably 10 to 50 rnass%, more preferably 15 to 40 mass%, based on 100 mass% of the resin solids content of the coating composition.
Examples of polyurethane resins include a polyurethane resin obtained by reacting an aliphatic and/cr aiicydlic diisocyanate, at least one diol selected from the group consisting of polyetherdiol, poi.yesterdiol and polycarhonatediol, a low molecular weight polyhydroyl compound and a dinethylol a.l.kanoi.c acid to form a urethane prepolymer; neutralizing the resulting urethane prepolyxier with a tertiary amine; dispersing the neutralized urethane prepolymer to be emulsified; mixing the resulting emulsion with an aqueous medium containing a chain extension agent1 a crosslinking agent and/or a quenchino agent as required: and continuing the reaction until the isocyanate group is substantially removed. This method generally produces a selfemuisif led polyurethane resin having a mean particle diameter of about 0.001 to 3 pm.
The amounL cf the polyurethane resin in t:ne aqueous coaning composition of uhe present invention is generally 2 to nass%, preferably 5 to 50 nass%, more preferably 8 to 30 mass%, based on 100 mass% of the resin. soIlds content o the coating composition.
&rinc.ceatJ.!) S The curing agent (B) is a coinpound that reacts with crossi 1 nkahie functional groups, such as hydroxy groups carhoxy groups, epoxy groups, etc, in the acueous:ilrrrforminq resin (A), to thereby cure the aqueous coating composition of the present inventioru Examples of the curing agent (B) include amino resins, polyisocyanate compounds, blocked polyisocyanate comprunds, epoxy-containing compounds, carboxy-containing compounds, carbodilmide group-containing compounds. etc. Among these, amino re-sins, polyisocyanate compounds and blocked polyisocyanate compounds, which react with hydroxy grouns, and carhodlimide group-containing compounds, which react with carboxy groups, are preferable. Pnino resins and blocked polyisocyanate compounds are more preferable. Amino resins are particularly preferable. Such compounds can be used singly, or in a comb that ion of two or more as the curing aqent (B) Usable amino resins include partially or methyloi.ated amino resins, obtained by the reactions of amino components with aldehyde components. Examples of the aiino components include inelamine, urea, benzoguanainine, acetoguanamine, steroguanamine, spiroguanami.ne, cicyandiamide, etc. Examples of aldehyde components include formaldehyde, paraformaldehyde, acetaldehvde, benzaldehyde, etc Methylolated amino resins in which some or all of the methylol groups have been etherified with suitable alcohols are also usable. Alcohols that cart he used for the etherification include, for example, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-hutyl alcohol, isobutyl alcohol, 2-ethyihutanol, 2-e-thylhexanol, etc. Preferable amino resins include melamine resins.
Particularly preferable amino resins include methyl-etherified rnelamine resins obtained by etherifyinq some or all of the methylol groups of partially or fully methylolated melamine resins with methyl alcohol; hutyl-etheri fled mel.amine resins obtained by etherifying some or all of the niethylol groups of partially or fui.].y methylo].ated melarnine resins iith butyl alcohol; and methylhutyl---etherifi.ed mel.ernine resins obtained by etherifying some or all of the methylol groups of partiali.y or fully meti-yloiated inelamine resins with methyl alcohol and betty].
alcohol. Among these, methyl-hutyl-etherified melamine resins are part icuiari.y preferable.
These melanine resins preferably have a weight average molecular weight of aboi.t 400 to about 6,000, more preferably about 800 to about 5,000, even more preferably about 1,000 to about 4,000, and most preferably about 1,200 to about 3,000.
In the present specification, the "numb r average
molecular weight." and the "weight. avenge molecular weight" of the film-forming resin (A) and th curing agent (13) are determined by measuring the retention time (retention volume) using Gel Permeation Chromatography (GPC), and converting the value into a polystyrene molecular amount based on the retention time (retention volume) of the standard polystyrene, which has a given molecular smount, measured under the same condition. More specifically, the "number average molecular weight" and the wweight average molecular weight" can he measured using an "HLC- 8120GPC" (manufactured by Tosoh Corporation) as a I Permeation Chromatography device at 40°C and a flow rate of 1 ml/rniri using four separation columns, "TSKgeI G-4000 HXL", "TSNgei 0- 3000 HXL", "TSKgel G25C0 HXL" and "TSKgel C-2000 HXL" (manufactured by Tosoh Corporation), tetrahydrofuran as an eluant, and a differential refractometer detector.
30. Commercial].y available melaxuine resins can he used as the melamine resin. Examples include commercially available products such as "Cyniel 202", "Cymel 203", "Cytnel 238", "Cymel 251", tymel 303", "Cymel 323", "Cymel 324", "Cymel 325", "Cymel 327", Cymel 350", "Cymel 3$5" "Cymel 1156", "Cyrnel 1158", "Cymel. I 6", "Cymel. 1130" (products of NihonCyt. ec Industries lncj, U-VAN 120", 0-VAI' 2OHS", 0-VAN 20SE60", "U-VAN 2021", "u-vAN 2028", "u-VAN 28-60" (products of Mitsui Chemicals, IncJ, etc. in the aqueous coating composiLion of the present S inventIon, it is preferable to use a hydroxy-containing acryli.c resin (A].), preferably a water-dispersible hydroxyl-containing acrylic resin (Al') and/or a core-sheJ.i.--type water--dispersible hyd.roxy-contaimnq acrylic resin (Al' ) , as the film--forming resin (A); and to use a melamine resin with a weight average molecular weight of about 1,000 to about 4,000, and more preferably about 1,200 to about 3,000, as the curing agent (B, to obtain a coating film with excellent flip--flop property and excellent water resistance.
when a. mei.am.ine tesin is used as the curing aoent (8 parato.luene sulfonIc acid, dodecylhenzenesulfonic acid, dinonylna:ht.halene suifonic acid, or like sulfbnic acid; monohiatyl. phosphate, di.hutyl phosphate, mono-2-ethy.].h.exyi phosphate, di-2-ethylhexyl phosphate or the like alkyl phosphoric esters, or a salt of these acids with an amine compound, can he used as a catalyst.
The blocked polyisocyanate compounds crc compounds obtained by blocking, with blocking agents; isocyanate groups of polyisocyanate compounds having at least two isocyanate groups per molecule. Examples of such blocking agents include phenol, creso.1, xylenol, nitrophenol, ethyiphenol, hydroxydiphenyl., hutyiphenol, isopropyiphenol, nony.iphenol, octylphenol, methyl hydroxybenzoate and like phenol-based blocking acients; E-caprolactam, 5-val.eroiactam, y-hutyro.lactam, -propiolactam and like lactam-base-d blocking agents; methanol, ethanol, propyl alcohol, hutvi alcohol, amyl alcohol, lauryl. alcohol. and like alipnatic aiconoi.-basea blocKing aqents ethylene qlycol monomethy.L ether, ethylene glycol rnonoethyl ether, ethylene giycoi En000hutyl. ether, d.ie.thyl.ene glycol ruonornethyl. ether, diethylene glycol monoethyl -ether,. propylene qlyccl monomethyl ether, methoxymethanol and like ether-based blocking agents; benzyi alcohol, glycolic acid, methyl glycolate, ethyl glycolate, hutyl glycolate, lactic acid, methyl lactate, ethyl lactate? butyl lactate, methyio]. urea, meti-tylol me.l.amine, dI.acetone alcohol, 2-hycIroxyethyl acrylate, 2--hydroxyethyl methacrylate and like alcohol--based blocking agents; fonnamide oxime, acetamide oxi.me, acetoxime, methyl ethyl ketoxime, diacetyl monoxime, benzophenone oxirne, cyclohexane oxirne and like oxime-based blocking agents; dimethyl rualonate, diethyl. rualonate, ethyl acet.oacetate, methyl. acetoacetate, acetylacetone and like active nethylene groupcontaining compound--based blocking agents; butyl rnercapt.an, te.rt-butyl. mercaptan, hexyl mercaptan, tert-dodecyl rnercaptan, 2-mercaptohenzothiazole th.i.ophenol, methyl.thiophenol, ethylthiophenol and like mercaptan-based blocking agents; acetanil ide, acetanisiLdide, acetotol.uide, ac.ryi.amide, methacrylamide, acetamide, stearamide, henzamide and like acid anide---hased blocking agents; succinimide, phthalirnide, maleimide and like imide'-hased blocking agents; diphenylamine, phenylnaphthylamine, xylidine, N-phenylxylidine, carhazole, ni, na.phthvlthrd tie, butylamine, dibutylamine, butylhenylamine and like amine--based blocking agents; inddazc.le, 2-ethylixnidazol.e and like inidazole-based blocking agents; urea, thiourea, ethylene urea, ethyi.enethiourea, diphenyiurea and like urea-based blocking agents; phenyl N-phenylcarhamate and like carhamate-hased blocking agents; ethyleneimine, propyleneinthe, and like urine--based blocking agents; sodium bisulfite, potassium bisulfite, and like sulfite salt ---based blocking agents; and azoi.e compounds etc. Examples of azole compounds include pyrazole and pyrazole derivatives, such as pyrazole, 3, 5-dimethylpyrazoie, 3--methylpyrazole, 4-henzyl-3, 5* -dimethylpyrazole, 4-nitro---3, 5-dirv.ethylpyrazoie, 4-hromo-3, 5-dianethylpvrazole, >-methyl---5---ohenylpyrazole, and the like; imidazole-and imidazole derivatives such as imidazole, benzimidazole, 2--rnethylirnidazole, 2-et:.hyi.imi.dazole, 2-phenylimidazole, and the like; imidazoline derivatives such as 2-methylimidazoline, 2-phenyiimidazoline, etc. Examples of pol.yi.socyanate corn ounds having at isaac two i.soc.yanate groups per molecule nciude heiLunethylerte diisocyanate, trirnethylhexamethylene diisocyartate, diner acid diisocyanate? lvsi.ne dilsocyanate, and like. ai.i.p-h.atic S dii.socyanate compounds; hydrogenated xylylene diisocyanabe, cyclohexylene diisocyanat.e, isophorone diisocyanate, and like alicyclic diisocyanate compounds; to.lyi.ene diisocyanate, phenylc-.ne dia.socyanar.e, 4? 4 -d.iphenyimethane d.isocyariate2 xvlylene dilsocyanaLe tetramethyixylylene dilsocyanate, napbtnaiene diisocyanat.e. and like aromat Ic dulsocyanate compounds; trivalent or higher organic polyisocyanate compounds such as 2-isocyanatoethyl--2, -dilsocyan&Locaproate, 3- isocyanatomethyl--]., 6---hexamethylene. diisocyanate, 4-isocyanatomethyl-l, 2-octamethylene dilsocyanate (commonly referred to as tr.iamino-nonane tr.iisocyanate); dimers and trimers of such polyisocyanate compounds; orepolymers obtained by urethani ration reactions of such polyisocyanate cornoounds with polyhydric alcohols, low-molecular--weight polyester t:esins, or water, under conditions auth that isocyanate groups are present in excess, etc. Examples of.-crbodiiide group--containing compounds include, for example, those obtained by the decarbonation reactions between isocyanate groups of the above-menti.oned polyisocyanate compounds. It is preferable to use, as the ca rhodi.iniide group-containing compound, a polycarbodilmide compound containing at least two carhodi.i.mi.de coups per moiecue.
The above-mentioned carhodi inide compounds are preferably water-soluble or water-dispersible poi.ycarhodiirride cc-mpounds, in terms of the smoothness, XI etc. of the resulting coating films. There is no particular limitation to the water-soluble or water-dispersihi.e polycarhodiimide compounds, so long as the polycarhodiimide compounds are stably dissolved or dispersed in an acueous medium.
Examples of the water**scC.uh.l.e polycathodi!mide compounds include Caihodilite SV-02", Carbodiilte V-02", Carhodi..1.ite V---02-L2", "Carhod.tli.te V04" (manufactured by Nissh.inbo Industries, Inc., trade names), and the like. Examples of the water-dispersb.1e polycarbodiiinide compounds include S CarhodiIite E---0l". tarbodilite E02" (manufactured by Ni.sshinho Industries, Inc., trade names), arid the Like.
Such cartodtiinide con'pounas can be usea singly, or in a combination of two or more.
It is preferable that the proportions of the aqueous fiim-formirig resin (A) and curing agent (B) in the aqueous metallic coating composition of the present invention be, based on the total. amount of these components, about 30 to 95 inass%, preferably about 50 to 90 nasal, and more prei-erably about 60 to BO mass% for the former; and about 5 to 70 nasal, preferably about 10 to 50 nasal, and more preferably about 20 to 40 macsI for the latter, to improve the smoothness, 001 and water resistance of the resulting coat-trig film.
Th.e amount of the curing agent (B) in the coating composition of the present invention is generally 5 to 50 parts by mass, preferably 10 to 50 parts by mass, more preferably 20 to 40 parts by mass, based on 100 parts by mass of the solids content of the resin component constituting the coating composition.
When the aqueous coating composition of the present invention comprises a hydroxy-containing acrylic resin (Al), the proportion of the hydroxy-containing acrylic resin (Al) is, based on the total amount of the aqueous filmfonning resin (A) and the curing agent (B), preferably about 2 to 70 mass%, more preferably about S to 55 massl, and even more preferably about 10 to 40 nasal.
ifthen the aqueous coating composition. of the present invention comprises the hydroxy-containing polyester resin (A2), the proportion of the hydroxy---containing polyester resin (A2) is.
based on the total amount of the aqueous fiira-formin resin (A) and the curing agent (B) , preferably about 2 to 70 mass%, more preferably about 5 to 55 mass%, and even snore preferably about to 40 snass%.
The aqueous costing composition of the present invention can be prepared by, for example, mixing the filim-fotming resin (A) and the copolymer (a), together with, if necessary, the curing agent (B) etc. in an aqueous medium using a Known nathan; and dissolving or oispersinq tne conponer.ts in the medism&.
Examples of usable aqueous media include water and organ.ic--sol.vent---ndxed solutions obtained by dissolving hydrophilic ornanic solvents in water. Examples of usable hydrophilic organic solvents include methyl alcohol, ethyl alcohol, isopropyl alcohol, propylene glyool monopropyl ether, ethylene glycol monohutyl ether, propy.lei.e glyco]. mono methyl ether, propylene gi ycol:nonobutyl ether, dipropylene glycol monomethyl. ether, dinroeyl.en.e glycol monohuty ether, tripropylene glycol monomethyl ether? 3-wathyl---3--methoxybutanol ctc Such media can be used singly, or in a combination of two or more. The proportion of the water and the organic solvent i.n the water and organic-solvent-rnixe.d solution is not particularly limited. However, the preferable amount of organic solvent is 1 to 50 mass%, more preferably 5 to 35 mass% The aqueous coating composition" -refers to a compositIon contrasted with the organic solvent coating composition, and generally represents a coating composition obtainable by dissolving and/or dispersing the fi]n---fonuing resin, ii pigment. etc. in water or an aqueous medium that mainly contains water. When the--oatin composition of the present invention is an aqueous coating composition, the water content of the coating composition is preferably in a range of from 10 to 90 mass%, more preferably 20 to 30 mass%, further preferably to 70 was s%.
The proportion between the fi1m-forminq resin-(A) and the copolymer Cs) is determined according to storage stability of the aqueous coating composition, appearance, coating performance (water resistance etc.) and the like of the resulting coating film. The proportion of the c:opolvrner(s) La preferably not less than 0.05 parts by mass, more preferably not ess than 0.1 parts by mass, further preferably not less than 0.2 parts by mass, and not more than 30 parts by mass, more preferably not more than 20 parts by mass, further pref:erably not more than 10 parts by mass, most preferabl.y not more than 5 parts by mass, based on 100 parts by mass of Lhe tim-forming resin (A) Further, in terms of storage stability of the aqueous coating composition, appearance, coating performance (wat:er resistance etc.) and the like of the resulting coating fin, the proportion of the copolymer (s) in the aqueous coatinc composition of the present invention is preferably in a range of.
13 from 0.01 to 15 parts by mass, more preferably 0.05 to 10 parts by mass, further preferably 0,1 to 5 parts by mass, based on 100 parts by incas of the aqueous coating composition.
Furthermore, when using, as the film-forming resin (A), the water-dispersible hydroxy-conLaining acrylic resin (Al') having an acid value of 1. to 100 mg KOH/g and a hydroxy value of 1 to 100 mg KOH/g obtainable through copolymerization of components (b-i) to (b-3) and also component (b-4) as necessary, the aw.Ieous coating composition of the present invention contains the copolymer(s) and the water-dispersible hydroxy-containing acrylic resin (Al') at the following ratio based on parts by mass of the resin solids content of the aqueous coating composition.
Copolymer: 0.05 to 20 parts by mass, preferably 0.1 to 10 marts by mass, more preferably 02 to 5 parts by mass; Water-aispersible bydroxy-containinq acrylic res in (Al') :. 2 to 70 parts by mass, preferably 5 to 55 parts by more preferably 10 to 40]parts by mass.
here, "che resin solids content of the aqueous coating -_7 4 composition" generally refers to the total content of the resin solids content of the copolymer Cs) and the water-dispersible hydroxy---containing acrylic resin (Al'), and the resin solids content of other resin(s) and the curing agent (B) added to the S aqueous coating composition of the present invention as required.
The reason why the aqueous coatin.g composition of the present invention containing a copolymer has the high viscosity and why the viscosity decreases with an increase in rate of shear, in particular, the reason why the viscosity is expressed and the viscosity decreased with an increase in rate of shear even in the aqueous coating composition containing a surfactant is assumed to be as follows. Since the polymer present in the side chain of the copolwner of the present invention contains a C4C24 alkyl-derived aroup, the hydrophobic interaction forms a network structure. This is conducive to the high viscosity.
Furthermore, the number average molecular weight of the polymer fails within a range of 1,000 to 10, 000, which indicates a relatively large volume of the polymer; therefore, the network st:ruct.ureis not easi.i.y suscept.ihl.e to the surfactant, It is further assumed that because the polymerizable unsaturated monomer (a) having a C4H24 alkyl group contains the ester bond in the irol. ecui.e, the polymer is not excessively hydrophobic despite the relatively large molecular weight, thereby suppressing aggregation of the side chain and forming the network structure due to hydrophobic interaction. It is further assumed that when the aqueous coating composition contains, as the film--forming resi.n (A), a resin having a ester bond, the viscosity is further developed by the formation of a network structure more strongly honded together by the high affinity between the ester bond in the film-forming resin (A) and the ester bond in the 04-024 alkyl-containing polvmerizahle unsaturated monomer (a) present in the side chain of a copolymer of the present invention.
If necessary, the aqueous coating composition of the present invention may contain additives for coating compositions, such as luster piqments, coloring piquients, extender pigments, hydrophobic organic solvents, curing catalysts, LIV absorbers, light stabilizers, pigment dispersants, antifoaming agents, plasticizers, surface control agents, antiaettlinq agents, etc. S Exarples of the luster pigments include aluminium (including evaporated aiLmunlum) copper, zinc, brass, nickel, aluminium oxide, mica, aluminium oxide coated with titanium oxide or iron oxide, mica coated with titanium oxide or iron oxide, etc Such luster pigments can be used singly, or in a combination of two or more. These pigments preferably have a scale-likeshape. Among these pigments, a]. umln.i.um, mica, aluminium oxide coated. with titanium oxide and iron oxide, and mica coated with titanium oxide or iron oxide are preferable, and aluminium is even more preferable.
Preferahi.y used sca lv luster pigments have a length in the longitudinal direction of about 1 to 100 pin, preferably about Sto 40 jim, and a thickness of about 0.001 to 5 pm, preferably about 0.01 to 2 pm.
When the aqueous coating composition of* -LIe present invention contains the above--mentioned luster pigment, ft is possible to forth an advantageous coa t:Lng fi n; liar i nq excellent luster with a high flip-flop property and reduced metallic mottling.
When the aqueous coating composition of the present invention contains the luster pigment, the content of the luster pigment is generally preferably about. I to 100 parts by mass, more preferably about 2 to 50 parts by mass, further preferably about 3 to 30 parts by mass, based on 100 parts by mass of the solids content of the film-forming resin (A) The aqueous coating composition of the present invention may further contain a phosphoric acid group-containing resin asaresin component, in addition to the above-mentioned film-forming resin (A) . In particular, when the aqueous coating composition of the present invention contains the above-mentioned luster pigment. especially an aluminium pigment, it is preferable that the aqueous coating composition of the present invention contain the phosphoric acid group-containing resin, in view of the smoothness, ECI, reduction in metallic mottling, and water resistance of the resulting coating film.
The above-mentioned phosphoric acid group-containing resin can be oroduced, for example, by ccvpolymerizing the pho5mhoric acid qroup-containing ooymerizabie unsaturated monomer and the other polymerizable unsaturated monomer by solution polymerization or other known methods. .xamples of the above--mentioned phosphoric acid group-containing polymerizabie unsaturated monomer in..c-1ude acid phosphoxyethyi meth} acrylate, acid phosphoxvpropyi (meth) acrylate, reaction products of glycidyl (meth)acrylate and alkyl phosphoric acid, etc. These can be used sing7y, or in a combination of two or more.
In the above-mentioned phosphoric acid group-containing resin, the mass ratio of the. above-mentioned phosphoric acid group-containing poierizabie unsaturated monomer to the other polymerizable unsaturated monomer in their copolymerization is preferably about 1/99 to 40/50, more preferably about 5/95 to 35/65, and even more preferably about 10/90 to 30170 -When the -aqueous coatinq composition of the present invention contarns the ahcve-mentionea phospnonc acid group-- containing resin, the amount of the phosphoric acid group-containing resin is prefezably about 0.5 to -15 parts by mass, more preferably about -075 to 10 parts by mass, and even more preferably about I to 5 parts by mass, based on 100 part-s by mass of the film--forming resin (A) -Examples of the coloring pigments include titanium oxide; Chinese white; carbon black; molybdenum red; Prussian blue; cobalt blue; azo pigments; phthalocyanine pigments; quinacridone pgrnent, isoindoline pignients; threne pigments; perylene pigments; dioxadine pigrmnts;-diketopyrrolopyrrole pigments, etc. These pigments can he used singly, or in a combination of two or more When the aqueous coating composition of the present invention contains the above-mentioned coloring pient, the amount of the coloring pigment as a solids coriter.tt preferably about; 1 to 200 parts by mass, more preferably about 2 to 50 parts by mass, and even more preferably about 3 to 30-parts by 5, based on 100 parts by mass of the fi.Jm-fornuLng resin (A) Examples of the extender piqments include talc, clay.
kaolin, bary La, barium sulfate, barium carbonate1 calcium carbonate, silica, alumina white, etc. When the acpeous coating composition of. the present i_U invention contains the above-mentioned extender pigment, the amomt of the extender piament as a solids content is-preferably shout I -to 200 parts by mass, more preferably about 2 to 50 parts oy mass, and even more preferably about 5 to 30 parLs cy mass-, based on 100 parts by mass of the filar-fonuing resin (A).
The hydrophobic solvent is preferably an organic solvent having a sotubility such that its soluble mass at 20t in 100 g of water is 10 g or less, preferably 5 g or less, and more preferably I g or less. Examples of such organic solvents include rubberS mineral spirits, toluene, xylene, 2.0 solvent naphtha, and like hydrocarbon solvents; ].-hexanol, 1-octano.i., 2-octanol, 2--ethylhexanol, 1-decanol., henzyl. alcohol, ethylene glycol. mono--2--ethythexvi ether, propylene g.l.ycol. mono-n-hutyl ether, dipropylene glycol xnono---n---butyl ether, tri.prooylene glvcoi mono-n-butyl ether, cropylene qlycol mono-2--ethylhexyl ether-, propylene glycol monophenyl. ether, and like alcohol solvents; n-butyl acetate, isobutyl acetate, isoamyl acetate, methylamyl acetate, ethylene qlycoi. monohutyl ether acetate, and like ester scl.ver:ts; and met:hyl isobuLyl ketone, cyclohexanone, ethyl. n-amyl. ketone, diisobutyl. ketone, and like ketone solvents. These organic solvents can be used singly, or in a combination of two or more.
To ensure excellent luster of the resulting coating film, it is preferable to use an alcoholic hydrophobic organic solvent as the hydrophobic organic solvent. among the above alcoholic hydrophobic organic soi.vents, it is preferahi.e t.o use at least one member selected from the -group consisting of 1- octariol, 2-oct.anol, 2 ---ethy].---l--hexano.l., ethyi.ene glycol mono2-ethylhexyl ether, propylene glycol monon-baLyl ether, and dipropylene glycol mono-n--butyl ether. 2-ethy13.hexanoi. and/ox ethylene glycoi mono--2---ethylhexyl ether are particularly preferable.
When the aqueous coating comoosit ion)f-the present -irvention contains the abovementioned hydrophobic organic solvent, the amount of the hydrophobic organic solvent is preferably about 10 to 100 parts by mass; more preferably about to 80 parts by mass, and even more preferably about 20 to 60 parts by mass, based on 100 parts by mass of the solids content of the aqueous coating composition.
The solids content of the aqueous coating composition of the present invention is generally about 5 to 70 nass%, * preferably about 15 to 45 tnass%? and more preferably about 20 to mass% To ensure excellent smoothness9 001 and luster of the resulting coating film, the viscosity V1 of the aqueous coating 2.0 composition of the present invention at 1,000 sec" and at 20t is preferably not more than 0.1 Pasec, more preferably in a range of 0.01 to 0.1 Paseo when the rate of shear is changed from 0.0001 secf' to 10,000 sec To ensure excellent smoothness; DOl and luster of the resulting coating film, the viscosity V2 of the aqueous coating composition of the present invention at 0.1 sec and at 20t is preferably in a range of 30 to 100 Pa-sec, preferably 35 to 70 Pasec when the rate of shear is chanoed from 0.0001 saC" to 1.09 000 sec'.
The viscosities V1 and V2 can be rmeasured using a viscoelastometer, such as a "HiKE P.heostress RSlSO" (product of HAAKE), The reason for the excellent smoothness, DOl and water resistance of the coating film formed by the aqueous coating compo ition of the present invention containing the water-- dispersible hydroxyl-containing acrylic resin (Al') or the core-shell-type water-ct! spersible hydroxy-containing acrylic resin (Al"), and the reason for the high flip-flop property, suppressed metallic mottling, and excellent luster when the S aqueous coating composition further contains a luster pigment are assumed to be as follows. The hydrophobic interaction between the hydrophobic group derived from the hydrophobic polymerizable unsaturated monomer present in the water- dispersible hydroxyl-containing acrylic resin (Al') or the core-shell-type' water-dispersible hydroxy-containing acrylic resin (Al") and the hydrophobic group derived from the C4-24 alkyl group present in the side chain of the copolymer of the present invention forms a network structure. This develops a characteristiá suh that the resulting aqueous coating composition has high viscosity, anif the viscosity decreases with an increase in rate of shear.. Such a viscosity characteristic is conducive to formation of a coating Lila having excellent smoothness, 1)01 and luster. Further, because the polymer in the side chain of the copolymer of;the present invention has a number average molecular weight ranging fran 1,000 to 10,000, which indicates a relatively large volume of the polymer, the network structure is not easily susceptible to the aurfactant generally used to disperse the water-dispersible hydroxyl- containing acrylic cesin (Al') or the core-shell-type,iater-dispersible hydroxy-containing acrylic resin (Al") in water. In this way, it is possible to maintain the optimum viscosity characteristic. It is further assumed that because the polymerizable unsaturated monomer (a) having a C4--24 alkyl group contains the ester bond in the moledüle, the polymer is not excessively hydrophobic despite the relatively large molecular weight, thereby suppressing aggregation of the side chain and forming the network structure by hydrophobic interaction. It is further assumed that the viscosity is further developed by the formation of a network structure more strongly bonded together by the high affinity between the ester bond derived from the monomer component present in the water-dispersible hydroxyl- containing acrylic resin (Al' or the core--sh&.l---t.ype water---dispersible hydroxy---containing acrylic resin (Al'') and the ester bond in the C4-C24 alkyl-coritaining polimierizable S unsaturated monomer (a) present in the side chain of a coolymer of the present invention, it is still, further assumed that the hydrophobic group derived f rem the hydrophobic pdlymerizable unsaturated monomer in the water-dispersible hydroxyl-containing acrylic resin (Al') or the core shell--type ater*--*dispersible 1.0 hydroxy-containing acryli.c resi.n (Al'') increases the water resistance of the resulting coating film.
The aqueous coating composition of the present invention can be applied on various substrates to be coated, thereby foriring coating films having an excellent appearance.
Substrates to be Coated The substrates to which the aqueous coating composition of the present inven ion is applied are not particularly limited. Examples of the substrates include exterior body panels of vehicles such as cars, trucks, motorbikes, buses, etc.; automobile parts; and exterior panels of i-.ome electric appliances such as mobile phones, audio equipment, etc. Among these, vehicle both exterior panels and automobile parts are preferable.
Materials ci these substrates are not particularly limited. Exampies thereof include iron, aluminum, brass, copper, tin, stainless steel, galvanized steel, zinc alloy Zn-Al, Zn-Ni, Zn-Fe, etcj steel, sheet, and like metal materials; resins such as polyethylene resin, polypropylene resin, acryl.onitri.le -butadiene styrene (ABS) resin, polyantide resin, acrylic resin, vinyli.dene chloride resin, polycarbonate resin, polyurethane resin, epoxy resin etc., various FRPs, and like plastic materials; glass, cement, concrete, etc. and like inorganic materials; wood; paper, cloth, and like fiber materials; etc. Among these, metal materials and plastic. materials are preferabie.
The substrate to he coated may he a metal mater!.a.l as described above or a v-ehicie body formed from such metal material, whose meLal surface has been subjected to a surface treatment such as phosphate treatment, chromate treatment, composite oxide treatment, etc. The substrate may also IJC sucn metal material; vehicle body, or the like as described above on which a*oatin: film is further formed.
Examples of the substrates on which a coating film is formed include one in which a surface. treatment is performed on the base material, if necessary, and an undercoating film is formed thareon; one in which an intermediate coating flu. is formed on the undercoating film; and the like. The ahove-described undercoating film is preferably a coating film formed by using electrodeposition coating materials, preferably cationic electrodepos.ition coating materials, Coating Method After forming a wet coating fIlm (uncured coating ftlm) by applying the aqueous coating composition of the present invention to a substrate, the wet; coating film is cured, thereby forminci a desired coating film.
The coating method of the aqueous coating composition of the present invention l.a not particularly limited, Examples thereof include air spray coating5 airless spray coating, rotary atomization coating, curtain coating, etc. A wet coating film can be formed by these coating methods, &nong these, air soray coating or rotary atomization coating is preferable in terms of improved smoothness, DOi, and flip-flop property of the resulting coating film as well as suppressed metallic mottling thereof..
Further, if necesary, static electricity way be used during coating The aqueous coating composition of the present invention is usua.ll.y appi led to a cured film thickness. of about I. to 50 pin, preferably about 3 to 50 pm, more preferably about. 5 to pm, further preferably about 3 to 25 pm.
A wet coating film can be cured by heating a substrate after the aqueous coating composition of the present invention is aool..ied to the substrate. Heating c;an be carried Out by known heating means. 2br example, drying furnaces such as a hot air furnace? an electrical furnace, an infrared induct.ion heating S furnace? and the like nay be used. The heating t.e:noerature is preferably about 80°C to 180°C, more preferabl.y about 10.0CC to 170°C, and further preferably about 12000 to 160°C. The heating time is not part cularly limited, and i.s usually preferably about :o to 60 minutes, further preferably about 20 to 40 minutes.
In order to prevent coating film defects such as popping and the ke, after application of the. *eous coating composition of the present invention, it is preferable to perform preheating, air blowing, etc. under heating conditions in which the coating film does riot substantially cure prio.r to the above-described heat. curing. The prehea ing temperature is preferably about 40CC to 100°C, more preferably about 50°C to 90°C? further preferably about 60°C to 80°C. The preheating time is preferably about 30 seconds to 15 minutes, more preferably about 1. to 1.0 minutes, further preferably about 2 to 5 minutes. Further, the above-described air blowing can usually he performed by blowing air of room temperature or air heated to a temperature of about 25°C. to 0°C to the coated surface of the substrate for about 30 seconds to 15 minutes.
When forming a multilayer coating film comprising a base coating film and a clear coating film on a substrate -sch as a vehicle body and the like by a two-coat one-bake method, the aqueous coating composition of the present i.n-enti.on can be suitably used as a composition for forming the base coating film.
A method of forming a coating film in this case can he carried out according to the below-described method 1.
Method 1 A method of forming a multilayer coating film, comprising the steps of: (1) applying the aqueous coating composition of. the present invention to a substrate to he coated to form a base coating film (2) applying a clear coating composition on the uncured base coat.ng film to f:or a clear coating film; and (3) heating the uncured brse coating film and uncured clear coating film to simultaneously cure both coating films.
The substrate i.n method I is preferably a vehicle body on which an undercoating film is formed; a vehicle body on which an undercoating film and an intermediate coating film are formed; or the like The. above-described undercoating ti I.m is preferably a coating film formed by using electrodeposition coating materials, and is further preferably a coating film formed by using cationic electrodeposition coating -materials.
In the present invention, the cured coating film refers to a film in a dry-hard condition according to JIS K 5600- 1-1 (2004) i e. a condition in which imprints due to fingerprints are not formed on the coated surface and no movement is de lected on the coatinc film when the center of the coated surface is strongly pinched with a thumb and an index finger, and in which scrapes are. unobservable on the coated surface when the center of the coated surface is rubbed rapidly and repeatedly with a fingertip. On the other hand, the uncu red coating film refers to a film that has not yet reached a dry-hard ccn.dition, including a film in a set-to-touch condition and a film in a dry-to--touch condi.I:..i.on accordincr to cc:s K 5600-i-i.
When the aqueous coating composition of the present invention is applied by the two--coat one-bake method of method I, the coating film thickness (the cured-film thickness) i.s pxeferah.1.y about 3 to 40 pm, more preferably about 5 to 30 pm, further preferably about S to 25 pm, further particularly preferably about 1.0 to 1.6 pin. Further, the c-Dating film thickness (the-cured film thickness) of the above-described clear coating composition is preferably about 10 to 80 pm, more preferably about 15 to 60 am further preferably about 20 to 45 pin.
Further, in method I, in order o prevent coating film defects such as popping and the like, after applidaticn of the above-described aqueous coating composition, it is preferable to perform preheati.ng, air blowing, etc. as described above tinder heating conditions in which the coating film does not substantially cure. Additionally, after application of the clear S coating composiui.on,itis possible, if necessary, to have an Jntervai of about 1 to 60 rn1 nutes at room temperature, or to perform preheating at about 40°C to 8000 for about 1 to 60 minutes.
-The aqueous coating composition and clear coating composition can be cured by using the above-described known heating means. The heating temperature is preferably about 8000 to 180°C, more preferably about 100°C to 170°C. and further preferably -about 120°C to 160°C, Further, the heating time is prefrah1.y about 10 to 60 minutes, ncr prei:erably about 20 to 40 minutes. Both coating films, La,, the base coat and the clear coat, can he simultaneously cured by such heating.
Further, when forming a multilayer coating fiTh.
comnrisi.ng a first colored coarA.ng film, a second colored coating film, and a clear coating film on a substrate to be coated such as a vehicle body or the like by a 3-coat 1-hake method, the aqueoi.s coating composa.ton of the present invention can he suitably used for forming the second colored coating film, A method of forming a coating film in 1± is case htay be carried out in accordance with the below-described method II.
ethod II A method of forming a multilayer coating film, comprising the steps of: (1.) applying a first coloring coating composition to a substrate to he coated to form a first colored coating film; (2) applying the aqueous coating corrosition of the present invention on the uncured first colored coating film to form a second colored coating film; (3) aplvin a clear coating comj-osition on the uncured second colored coating film to form a clear coating film; and (4) simultaneously heat-curing the uncured first colored coating film, uncured second colored coating film, and uncureci clear coating film.
in method Ii, the method of forming a coating flint in method I is carried out on the uncured first colored coating film.
S Preferred substrates in method Ii include a vehicle body and the like having an undercoating film formed thereon. The above--described undercoating film is preferably formed by using electrodeposition coating materials, and further preferably formed by using cationic electrodeposition coating materials.
1.0 in method Ii, the r atinorLun thickness (the cured film thickness) of the firsI-coloring coating composition is usually preferably about 3 to 50 urn, more preferably about 5 to pm, and further preferably about 10 to 25 pm. Further, the coating film thickness (the cured film thickness) of the aqueous coating compost..on of the present invertuio is preferably about 1 to 30 pm, more preferably 3 to.25 pm, further preferably about to 20 pm Additionally. the coating film thickness (the coating film thickness-) of. the clear coating composition is usua.Ii.y preferably about 10 to 80 pm, more preferably about 15 to $0 pm, furthr preferably about 20 to 45 pm.
Specific examples of method II include the following methods 11-1, II-2, and the like.
Nethod Li-i A method of forming a inuitilayer coating film, comprising the steps of (1.) treating the surface of a steel. plate if necessary, and applying an electrodeposition coating material thereon, followed by heat-curing, to torn a cured electrodeposition coating film; (2-applying a first coloring coating composition on the cured electrodeposi.tion coat ag film obtained in step (1.) in an intermediate coating booth to form an intermediate coating film; (3) applying the aqueous coating composition of the present invention on the uncured intermediate coating film obtained in step (2) in a base coating booth to form a base coat; (4) applying a clear coating material, on the coated surface of the base coat obtained in step (3) in a clear coating booth to form a clear coating film; and (5) heating the intermediate coating film, base coat, and clear coat formed in steps (2) to (4), thereby simultaneously curing these three coating films.
Note that the above-described booths are facilities to maintain the coating envaronment conditions such as temperature, humidity. etc. within, a certain range in order to ensure un:i.form coating quality. Usually, different booths are used according to the type.s of coating materials to he applied. dditi.ona ly, in order to prevent sagging, unevenness, and the like of the coating material applied to a. substrate, there are cases where the same coating materal is applied to the substrate two separate tines in the same booth. En this case, Ci nt time coat ing is referred to as a first--stage coating, arid second-time coating is referred to as a secondstage costine.
in method il-i, the coating film thickness (the cured film thickness) of the first coloring coating composition is usually preferably about 5 to 50 pm, more preferably about 10 to 30 urn, further preferah1.v about 1.5 to 25 pm. Further, the coating film thickness (the cured film thickne s) of: the aqueous coating composition of the present invention is preferably about 3 to 30 pm4 more preferably about5t a 25 pm, further preferably about 8 to 24) pm, further particularly preferably about 9 to 14 pm.
Additionally, the co.uting film thickness (the cured film thickness) of the clear coating composition is usually preferably about 10 to 80 put, more preferably about 15 to 60 pm, further preferabi.y about 7.0 to 15 Further> when the aqueous first coloring coating composition i.sused as the first coloring coating compositIon in metnod ti--i, after application of tne aqueous first coloring coating composition, it is preferable to nerform preheating air blowing, etc. as described above under heating conditions in which-the coating film does not substantially cure in order to prevent coating film defects such as popping and the like.
-SF
Method li-2 A method of forming a muitilayer coating film, comprising the steps of: (1) treating the surface of.. a steel, plate if necessary, and S applying an electrodemosition coating material thereon, followed by heat-curing, to form a coating film; (2) applying a first base coatinrj material. on the cured electrodeposition coating film obtained in step (I) at a first stage in a base coating booth to form a first base coating fi.lr.n; (3) applying the aqueous coating composition of the present invention on the first base coating film obtained in step (2) at a second stage in a base coating booth to form a second base coating film; (4) applyinq a clear coating material on the second base coating film obtained in suep (3) in a clear coat:i.ng booth to form a clear coating film; and (5) heating the first base coating film, second base coating film, and clear coi dng film formed in steps (2) to (4), thereby simultaneously curing these three coating films.
In method 11-2, the coating film thickness (the cured film thickness) of the first coloring coating composition is usually preferably 3 to 40 pm, inure preferably about; 5 to 25 pin, further oreferably about 10 to 20 pm. Further, the coatina finn' thickness (the cur" d I-un thickness) of the aqueous coating composition of the present invent ion i.e pref rably about I to 25 pm, more preferably about 3 to 20 pm, further preferably about 5 to 15 l,un.. Additionally, the coating film thickness (the cured film thickness) of the clear coating composition is usually preferably 10 to 50 pm, more preferably about 15 to 60 pm, further preferably about 20 to 45 p.m.
In the coating method of method ib-2, the intermediate coating booth is unnecessary. Accordingly, rnet'.hod I is advantageous in that the energy for controlling temperature and humidity in the intermediate coating booth can be reduced.
Further, in the coat log method of method 11-2, the.
first coloring coating composition and the aqueous coating composition of the present invention are applied in the base coatinq booth. Accordingly, a heating appliance is usually not installed between application of the first coloring coating composition and api.ication of the aqueous coating composition of the present inventJon; and generally, the above-described preheating is not perfonned on the first base coating film that is formed by application of the first coloring coating composition. Consequently, method IT 2 is advantageous in that it tO can reduce the energy for preheáting. Accordingly, in view of energy--saving, it is preferable that the coating method in method IT.-2. does not include a heating step between application of the first coloring coating composition and application of the aqueous * coating composition of the present invention.
Further, in method II, after application of the aqueous coating composition of the present invention, it is * preferable to perform preheating, air blowing, etc.s described above under heating conditions in which the coating film does not substantially cure in order to prevent coating film defects such as popping and the like. Additionally, after application of the clear coating composition, it is possible, if necessary, to have an interval of about I to 60 minutes at room temperature, or to perform preheating at about 40°C to 80°C for about 1 to 60 minutes.
The three--layered coating films, ie., the above-described uncured first color-ed coating film, uncured second colored coating film, and uncured clear coating film, can be heat-cured by the above-described known heating means. The heating temperature is preferably about 80 to 130°C, more preferably about 100 to 170°C, further preferably about 120 to I 0 C. Further, the heating time is preferahl.y about 10 to SO minutes, more preferably about 20 to 40 minutes The three-layered coating films, ie, the first colored coating film, second colored coating, film, and clear coating film, can be simultaneously cured by such heating.
Any thenncsettipg clear coating composition known as a composition for coating vehicle bodies and the like can he used as the clear coating composition used in methods I and II Examples thereof include organic solvent-type thermosett.ing coating compositions, aqueous therinosetting coating compositions powder theniosett.ing coating compositions, and the like, which comprise a crosslinking agent and a crosslinkable functional group-containing base resin.
Examples of cross linkable functional groups contained in the base. resin include carhoxy, hydioxy, epoxy, sil.anol, and the like. Types of base resins include, for example, acrylic resins, polyester resins, alkyd resins, urethane resins, epoxy resins, fluorine resins, and the like. Examples of crossli.nking agents include polyisocyanate compounds, blocked polyisocyanate compounds, melamine resins, urea resins, carboxy-containing compounds, carhoxy-contain.ing resins, epoxy-containing resins, epoxy--containing compounds, and the like.
Preferable combinations of the base resin/crosslinking agent in the clear coating composition include carboxy-containinq resin/epoxy-containing resin, hydroxy-conta.ining resin/polyisocyanate compound, hydroxy-containing resin/blocked polyisocyanate compound, hydroxy-containing resin/meLnine resin, and the like.
Additionally, the clear coating composition may be a one-component coating material, Or a multiple-component coating material such as a two-component urethane resin coating material., etc. Further, if necessary, colorin.g pigments, luster pigments, dyes, etc. may be added to the clear coating composition, without impairing the transparency thereof. Still further, extender pigments, UV absorbers, light stabilizers, antifoaming agents, thickening agents, :anticorrcsives, surface control agents, etc. may also be suitably included.
As the first-o1oring coating compositions used in method ii, -for example, a known thermosett ing internediate coating composition can ne used in method Il-i, ana a known * thermosetting base coating composition can he used in method II2, Specifically, for example, a thenn.osett.ing coating composition containing a crossli.nkable functional qroup-containinq base resin, crosslinking agent, coloring p.Lyaent, and extender oigmer.t may he suitably used.
Examnies of crcsslinkable functional groups present in the base resins include carhoxy, hydroxy, epoxy, and the like.
Types of base resins include, for example, acrylic resins, polyester resins, alkyd resins; urethane resins, etc. Examples of crosslinking agents incTude nei.amine resins, polyisocyanate compounds, blocked polyisocyanat.e compounds, etc. n.y of organic soivent-twe coating compositions, aqueous coating compositions.
and powder coating compositions may be used as the first coloring l.E coating composition. mong these, an aqueous coating composition is preferably used.
In methods I and 1.1, the first coloring coating composition and the clear coating composition can he applied by any known method. Examples oi such methods include air spray coaLing, -afrless spray coating, rotary atomization coating, and the like.
[Examples I
Hereinbelow, Lia present invention is described in further detail with reference to Production Examples, Examples, and Compar Live Examples. However, the present invention is not limited thereto. In each example, part (s) and " are based on mass unless otherwise specified. Additionally, the film thickness of a coating film is on a cured basis Production of Macromoncmer (mi.)
Production Example I
16 parts of ethylene glycol monohutyl ether and 15 parts of 2, 4diphenyl-4---methyl--l--ventene (he.rereinheiow, sometimes abbreviated as "MSD were placed into a reaction vessel equipped with a thermometer, athennostaL, a stirring device, a ref lux condenser, a nitrogen gas introducing pipe, arid a dropping funnel. The mixture was heated to 160CC under stirring while nitrogcn gas was blown into the vapor space oIl the vessel.
When the temperature reached 1601'C, a mixture comprising 30 parts of n-butyl methacrylate, 40 parts of 2-ethyihexyl methacry].ate, 3D parts of 2-hydroxyethyi. methacrylate, and 7 parts cf di-tert----amyl peroxide was added dropwise thereinto over 3 hours; and the resulting mixture was stirred at the same temperature for 2 hours.
Subsequently, -the resulting mixture was cooled to 30°C, and diluted with ethylene glycol monobutyl ether, thus obtaining a niacromonomer solution (m---1----i) having a solids content of 65%. The hydroxy value of the obtained macromonomer was 125 ing KOFI/g. and the number average molecular weight thereof was 2,300. In addition, according to an analysis by proton NMR, 97% or more of ethylene unsaturated groups derived from MSD were located at the ends of a polymer chain, and 2% thereof disappeared. Note that the above--described analysi.s by proton NNR was carried out in the -following maniter. Using heavy chloroform as a solvent, the following peaks before and aft-er the polymerization reaction were measured: peaks based on protons of unsaturated groups in MSD (4.8 ppm, 5.1 ppm); peaks based an protons of ethylene unsaturated groups aL--the ends of a macromonomer chain (5. 0 PPm, 5.2 ppm); and a peak of aromatic protons derived from MSD (7.2 ppm). The aromatic protons (7.2 ppm) derived from the above- 23 -described M30 was assumed to stay the same before and after the polymerization reaction. Using this value as a reference, each unsaturated group (unreacted, rnacromonomer chain end, disappeared) was quantified.
Production xamp 3 to 1. 7 Synthesis was carried out in the same manner as in Production Example 1, except that-the composition shown in -Table I was used, thereby obtaining macromonomer solutions (rn-I--i) to (m-l-17) having a solids content of 65%.
Table 1 shows the composition of raw materials (parts), proportion of a polymerizable unsaturated monomer (a) having a C4---C24 alkyl. group in a nionorner component (I), hydroxy value (mg KOH/g) and nurther average molecuia: weight of the ruacromonomet solutions (rn-i--i) to (m-i--17)
S [Table I]
iabi I-i ________________________ Piuctorxarn3Ja 4 tAarnmnnmer S3ut3on ny-i-I rn-i-? -0-3 m-i-4 rn-I-S m-i-4 rn-3-7 n-i-2 rn-i--9
-
_____________-UL.!L!LJLJL.JL JL 35 35 3.5 33 35 35 14) 2 --fl----'------jrrbt wsr4&, 50 PoEiw,hk s.., r; c.arnr (,) hwktg n C 8bnkta -. . ._. --..
_________ -40 Sta,M cthwvlat -25
-
2-h ---poIrnriab Jr,sturatd Y 30 20 25 40 40 40 25 25 25
--
0-t-am4 par dn 7 7 1 Axob scutyyori&t 7 7 I --1*1) 150 i0 i;r 121 120 44) 140 160 Contant z4tnsthrathWhionornar(a53nicin gnr Cwnpene2at (0) 75 60 13 40 -20 10 75 7$ 75
-
Hy4i3moi Viuo [,soH/J -125 53 104 367 -!67 F 67 01 004 lOT -tbervernScularweht fl 2200 flO(0 2 74001240QtTt $000 7900 Tab!e 1 -2 -- --r -----IS 01 I? --.Ioioi_j ii I 1acoinorft,rner S&uto;i rn--i--IG n-I--10Irn-l--i2 nr-1-33rn--1-14rn--1--4 m---15Irr-0--0 7 --_----_----_______ ________________ ________________ *.-__-_._- Ethyan gvcS nxrn?j,stvi athr 16 IS 34 16 15 10 18 -10 - 2Siirnh;F4-cnoThvI--nth,a --1.0) fTT TIj7 T Ti t*tCC $LoacoQ Glsn,,ocizb0a unatrtS -54) 43 24aIko,ouu 2*t?w*cs3 85 50 55 45 0 -
---
Monornac ----------------------.-*---------t--.---cornaonar3t o-o,--oontw, -25 7 -20 12 25 25 polcrcanehEn,rtu-aed - ryinornsr 2drl,o,ropy3 ------ ---n,ath.c,-ylsta --- --tart-arn4prox0d 1 z.Li._1. -Arob -sobutvrornt, s 1 Tcrcii-r, ti 160 160) 160 ISO 101(3 120 iSO 1010 -
---
Cor.o(rnnnt(1) 5 t -0 -a -D292i5 32 0 iSO 107 Wsjmber average rnaOecu3r w&5ht ____________ ______ 9.0-30 I 2.300 2.300 2.301) 2300 2.3001 4)00 -I.00 -lu (Note) -"Acryester SL" pronuct name, nianuractured by M.itsuriisni Rayon Co., Ltd., a mixture off dodecyl methacrylate and tridecyl 93..-xnethacry.i ate.
Production Example 18 carts of ethylene glycol. monohutyl ether was placed into a reaction vessei equipped with a thermc,meter, a thenwstat, a stirring device, a refhix condenser, a nitrogen gas introducing pipe, and a dronping funnel. The mixture was heated to 130°C: under at arcing while nitrogen gas was blown into the vapor space of the vessel. When the temperature reached 130°C, a mixture comprising 30 parts of n-hutyl rneLhacrylaWe, 40 pans of** 2-e.thylhexyl methacrylate. 30 parts of 2 hydroxyethyl methacrylate, parts of 3mercaptopropionic acid, and 4 parts of 2,2'-azobis(2-ntethylbutyronitrile) was added dropwise thereinto over 4 hours; the resulting mixture was stirred at the same temperature for i hour; and further, a mixture comprising 0.5 parts of 2,2'--azohis (2-methyibutyronitrile) and 3 parts of ethylene glyccl monobutyl ether was added dropwi.se thereinto over 1 hour.
Stthseuuently, the resulting mixture was cooled to 30C, thereby obtaining an acrylic resin solution having a solids content of 70%. 67 parts of glycidy]. methacrylate, L02 parts of 4-tert--butyl.pyrocatechol, and 0. 1 parts of N, N-diinethylaminoethancl were added to the obtained acrylic resin solution; and air was blown into the liquid, followed by heating to 110°C under stirring.
When the temperature reached 110°C, the resulting mixture was stirred at the sanie temnerature for 6 hours. Subsequently, the zh resulting mixture was cooled t.o 30"C, arid thlutea with ethylene.
glycol monohutyl ether, thus obtaining a macromonomer solution (m-i--l8) having a solids content of 65% The hydr.cxy value of the obtained macromonomer was 147 mg KOHIg, and the nuniber average molecular weight thereof was 2,400, Production Example 19 parts of diethylene glycol monoethyl ether acetate was placed into a reaction vessel equippedwi th a thermometer, a thermostat, a stirring device, a reflux condenser, a nitrogen gas introducing pipes and a dropping funnel. The mixture was heated to 130°C under stirring while nitrogen gas was blown into the vapor space oi: the vessel. When the temperature reached 130°C, a mixture comprising jO pdrts of n--xuty± methacryLe, 50 parLs of 2ethylhexyl. methac.rylate, 4 parts of 2ruercaptoet.hano1, and 4 parts of 2, 2' -azohis (2-methylbutyroritri 1) was added dropwise thereinto over 4 hours; the resulting mixture was stirred at the same temperature for 1 hour; and further, a mixture comprising 0.5 øarts of 2,2' --azohis (2---methylbl.2tyronitriie) and 3 parts of diethylene g.iycol monoethy.l ether acetate was added dropwise thareinto over I hourS Subsequently the resulting miixture was 1(3 cooled to 30°C, thereby obtaining an acrylic resin solution having a solids content of 70%. 7.6 parts of 2isocyanatoethyl met.hacryiate (product name; Karenz M0l!, manufactured by Showa Denko K.K.) and 0.02 parts of 4---tert--utylpyrocatechoi were added to the obtained acrylic res.xn solution; and au was blown into the liquid, followed by heating to 90°C under stirring. When the temperature reached 90°C, the mixture was stirred at the same temperature for 5 hours. Subsequently, the resulting mixture was cooled to 30°C, and diluted with diethylene glycol monoethyl ether acetate, thus obtaining a macromonomer solution (m-1--19) having a solids content of 65%. The hydroxy value of the obtained macromonomer was 0 rug KC1-i/g, and the nurder average molecular weight thereof was 2,300.
Production Example 20 24 parts of ethylene glycol monohutyl ether and 4 parts of 2,4diphenyl-4--methyll-pentene were placed into a reaction vessel eipped with a thermometer, a thermostat, a stirring device, a reflux condenser, a nitrogen gas introducing pipe, and a dropping tunnel The mixture was heated to 150°C under stirring while nitrogen gas was blown into the vapor space of the vessel. When the temperature reached 150°C, a mixture comprising 15 parts of n-hutyl methacrylate, 20 parts of 2-ethylhexyl methacrylate, 15 parts of 2-hydroxvethyi methacrylate, and 3 parts of ditert-amyl peroxide was added dropwise thereinto over 3 hours, and the resultinci mixture was stirred at the same temperature for 1 hour and 30 minutes. Subseauentiy, the resulting ixtur was cooled to 115°C, and diluted with 4.5 parts of ethylene glycol rnonobuttyl. ether. Next, a mixture comprising 15 parts of n-butyl methacrylate, 20 parts of 2-ethvlhexyl methacrylate, 15 parts of 2-hvdroxyethyi. methacrylate, and 0. 6 S parts ci azobisisobutyron.ttrile was added dropw.ise thereinto over 2 hours, and the resulting mixture was stirred at the same temperature for 30 minutes. Eurthe, a mixture comprising 0,25 parts of azobisi.sobutyronitril.e and 5 parts of ethylene glycol monobutyl ether was added dropwise therei.nto over 1 hour9 and the resulting mixture was stirred at the same temperature for 30 minutes. Subsequently, the resulting mixture was cooled to 30°C, and diluted with 22 parts ot ethylene glycol monobutyl ether, thus obtaining a macromonomer solution (m'-1--20) having a solids content of 65%. The hydroxy value of the obtained.macrornonomer was 125 mg OH/g, and the number average molecular weight thereof was 2,300.
Production Example 21 24 parts of ethylene glycol. monobutyl ether and 3.5 parts of 2, 4diphenyi"4'methyl--i---pentene were olaced into a reaction vessel equipped. with a thermometer, a thermostat, a stirring device, a ref lux condenser, a nitrogen gas introducIng pipe, and a dropping funnel, and heated to i60°C under stirrinc while nitrogen gas was blown into t.rIe vapor space of the vessel When the temperature reached i60C, a mixture comprising 40 parts of 2-'ethy1hexy.1 methacrylate, IC) parts of 2'-hydroxyethyl methacrylate, and 2.6 parts of di-tert-'amyl peroxide was added dropwise thereinto over 3 hours, and the resuitinc mixture was stirred at the same temperature for 1 hour and 30 ndnutes, Subsequently, the resulting mixture was cooled to 120°C, and diluted with 4.5 parts of ethylene glycol monobutyl ether, Next, a mixture comprising 40 parts of 2ethyl.hexy1. methacryi.ate, 10 parts of 2"hydroxyethyl raethacrylate, and 0.6 parts of azdbisisobutyronitrile was added dronwise thereinto over 2 hours, and the resulting mixture was stir.r.ed at the same temperature for 30 minutes. Next, a mixture concrising 0.25 parts of azobisisobutyronitrile and 5 carts of ethylene glvcol inonobutyl ether was adcieo dropwise tnereinto over 1. nour, and the resulting mixture was stirred at the same temperature for 30 minutes.
Subsequently, the resulting mixture was cooled to 30°C, and S d.ilut.;ed with 22 parts of ethylene glyco]. monobutyl ether, thus obtaining a macromonomer solution (m-1--21) having a solids content of 65%. The hydroxy value of the obtained macromonomer was 83 Rig KOH/g, and the number average molecular weight thereof was 2,200.
Example 1
154 parts (solids content: 10 parts) of the macromonomer solution (m-4--l.) obtained in Production Example 1, parts of ethylene iycol motohutyl ether and 30 parts of diethylene glycol monoethyl ether acetate were placed into a reaction vessel equipped with a thermometer, a thermostat, a stirring device, a ref l.ux condenser, a nitrogen gas introducing pipe, arid two dropping funnels; and heated to 85°C while nitrogen gas was blown into the liquid. Subsequently, the following mixtures were simultaneously added dropwise over 4 hours to the reaction vessel, maintained at the seine temperature: a mixture comprising 31.5 parts of N, N-dimethyl. acrylamide 31.. 5 parts of N-isopropylacrylanilde, 27 parts of 2-thydrcxyethyl acrylate, 10 parts of. ethylene glycol monobutyl ether, and 40 parts of diethyi.ene gi.yco]. monoethyl ether acetate; and a mixture comprising 0.15 parts of Perbuty1 0" (product name, manufactured by NOF Corporation, polymerization initiator, tert-hutylperoxy--2-ethyihexanoate), and 20 parts of ethylene glycol monobutyl ether.
After completion of the dropwise addition, the mixture was stirred at the same temperature for 2 hours for aging.
Subsequently, a mixture comprising (L3 parts of 2,2'-azobis(2,4--dimethylvaleronitrile) and 15 parts of ethylene glycol monohutyl ether was added dropwise over 1 hour to the reaction vessel maintained at the same temperature. After completion of the dropwise addition, the mixture was stirred at thes*me 9.7 temperature for 1 hour for acing. Subsequently, the resulting mixture was cooled to 30°C whi i.e adding ethylene giyco.I. r.nonohutyl ether thereto, thereby obtaining a copolymer solution having a solids content. of 35%. The weight average molecular weight, of the obhained copolym.er was 31X1. 0. 215 parts of deionized water was added to the obtained copolymer solutioi, thereby obtaintnq a diluted fluid of copolymer (RC--1) having a solids content of 20%.
Examples 2 to 25 and Comparative Examples i to 5 Synthesis was carried out in the seine manner as in 1.0 Example 1, except that the mpositiori shown in Table 2 was used, thereby obtaining diluted fluids of copolym.er (RC-2) to (RC--30) having a so iris content of: 20%, Table 2 below shows the comoosi. c.:Lo:n of raw materials (parts) and weight average molecular weight of the diluted fluids of copolyner (RC--l) to (RC-30)
Table 21
Thbk* 2 ____________ ______________________________ .>,tL RS - 8O2frC °-N PRC-RC- _____________ _____ -r'--'------ml r ml m3 MarJN,nor mr-U sc,5s0 in 2 34 8 ______KkmMv54Th4 141J!i T'j 1541 1e4 EennEa N N P d.m.r-v1*mid 31 315 3 [35 a 33 31.3 13 J V int,n (n.th -.----.-----.i.-.
nonomr -.31.5 81.5 81M 21.5 22 31.5 45 35 13 4_. ------Lm-2j 2-tv,dr.atF, ,ylctrs 15 7? 2. 7? IL 25 2 e 2/ 851813 813 818 815 WI Q5'J 015 WI 0 -10 -18!8 10 5 -0 13 1 50 U? 50 mi!rom2r ha.,cn *cç1ii vats, Cm- fl'
-
of.,tra p;;zb1t wgirt4 ycneaimz Sm 11 2 0 S 0 0 _________ Q?:a1 7ifl Tohlc 2--Z ________
ZL S
3 Ad Pu,(Cp*lrncu 2 *1 10 EU 1 --l-'-n-1-t sc-i--3cn-l-n-1-II 2 312t2t22 34 35.4 S4.6.4 14 11I 41.43ltSAta4 27? s 1 S U 1 u3 315 53t 287
S
MarmCcsponect cctcrM,:I 4K-.,st&-AM-300 SI m0rnr?vuc. . ydccah:!cu c-ocJ -. -.
(cp-2) .----------------------- »=-kacrt2t3 sststa a 431 2? 17 30.-7 2? 246
I
t*fl1tu moncak tnsa31jirnd J L__._._ Ln L4L ii3»= fl.&!& qjj 10 10 10 10 10 18 j* 18 12 -0 tact o a zul,ta unsatntS nonecrar ?cvr'g Ewc3opclc grow I 77 T T dvcago cc uwbtil3 3131 fl$j3 11 31 23 Tahi 2-3 ComerabEarnp.
0uttdFluc>fCopovmsr. FI1 $ j: R2 2 ta--1--ov-1--m-1--tyr-1-- 1scscacr or 3 solut 4 3 3 5 8 _______ ___ i 2!! 2!. 2!! i?.
IS'S t-wb1.SSP1d4 26 435 115 335 335 335 1 (p) usaorats 1 - 35fl 3133fl70t*fl'28 lu bnl*' ctg 26 315 115 333 335 315 l
--L L
23.22! V 2? 27 27 27 200 (354) 012 010 015 01(3 01(3 0 1 frasrn,nonis (r3j tMaas % 25 0 10 lEi 1C 30 0 10 10 c ururabEe drcaatlcrMS rcKromsr huwcc-uo a,srshop uclc jotiçi 300 0 0 to'pe,t of othur Pc mgczab3e unsawrated caonoo era (v [Mass %] 0 0 0 0 0 0 0 1W&oht orogs nmEcctc3arwoiht [uc10J 70 8 12 1 35 42. 31 31. 28 V Tnb!e 2-4 Dktod AtM of Copob'rner RC---30
--
--
Mavro,nonorner On-i) sohgton ---Ouantñy Monomer - Crnnponent (m) mononnr having -hydropiUc group (nr-2) -20 Other pdyrnethable unoaturatS cnoncmers Cm-Methyl methcrylate 30 3) ---Ethyl_aoryate -ca c -cccaaacaa acc PerbjbgFO -015 Content of marremon;m; - Conter,t of p&ynrnrizaS unoturatod anonomer Ievhig a hydrophIk group (rn-2) }Mss --70_ Content of other p y(nerftable unatu,ated rnorlomen CurS) [Ma55 %] 40 West average rcolewar weght [ioJ 31 (Note 2) NK-ester N4-90G°: product name? manufactured by Shin---Nakamura Chemical Co., Ltd; a polymerizable unsaturated menomer S having a polyoxyalkylene chain; in the General Formula (1), RL j a hydrogen atom, R is methyl, f3 is ethylene, and in is c;and the molecular weight is 454, (Note 3) "PLEX 6954-0: product name, manufactured by Degussa; a mixture comprisIng 20% of deionized water, 20% of methacrylic acid? arid 60% of polymerizable unsaturated monomer having an aikyl group and a polyoxyalkylene chain (in the General Formula (1), 8' is methyl, 1*2 is C] 6--lB alkyl, R is ethylene, and n is 25; and the molecular weight is about 1,422).
Rrothw±icoRroxycontathir9AcryJj.cResi.n(Al) :15 Production Example 22 128 part-s of deionized water and 3 parts of "Adekaria Soap SR-1025° (product name, manufactured by ADEKA, emulsifier, active ingredient 25%) were placed into a reaction vessel equipped with a thermometer, a thermostat:, a stinina device, a reflux condenser, a nitrogen gas introducing-pipe, and a dropping funnel. The mixture was stirred and mixed in nitrogen flow, and heated to 80°C.
Subsequently, 1% of the entire. amount: of monomer emulsion for the core portion, which is described below8 and 5.3 parts of a 6% ammonium persulfate acfueous solution were introduced into the reaction vessel, and maintained therein at S0't. for 1.5 minutes. Thereafter, the remaining monomer emulsion for the core portion was added dropw.ise over 3 hours to the -reaction vessel maintained at the same temperature After completion of the dropwise addition, the mixture was aged for i hour. Subsequently, the be..ow-desc.ribed monomer: emulsion for the shel.1. portion was added dropwis to the reaction vessel, over 1 hour, followed by aging for 1 hour. Thereafter, the mixture was cooled to 30CC while gradually adding 40 pefl:s of a 5% 2-Cdimethylamino ethanol aqueous solution thereto, and filtered through. a 1.00-mesh. nylon cloth, thereby obtaining a water--dispersible hydroxy-containing acrylic r in water dispersion (Al-i) having a mean particle diameter of 95 run and a solids content. of 30%. The obtained water-dispers.ihi.e hydroxy--contai.n.ing acrylic resin had an acid value of 33 mg KOH/g, and a hydroxy value of 25 mg KOH/g.
A monomer emtii.si.on for the core portion: 40 parts of deionized water, 28 paits of "Adekaria Soap SR-i025', 21 parts of methylene bisacryla2mide, 2J3 parts of styrene, l4'-i parts of methyl methacrylate, 26 parts of ethyl acrylate, and 21 parts of n-butyl aorylate were mixed and stirred, thereby obtaining a monomer emulsion for the core portion.
A monomer emulsion for the shell portiont 17 parts of deionized water, 1.2 parts of Adekaria Soap SR-1025", 003 parts of anurnni.um persulfate, 3 part.s of styrene, 5.1 parts of 2-hvdroxyethyl acryi.ate, 5. parts of methacryli.c acid, 6 parts of methyl methacrylate, L6 parts of ethyl acrylate, and 9 parts of n-hutvl acrylate were mixed and stirred, tier..eby obtaining a monomer emulsion for the shell portion.
?roductiort Examples 23 to 26 Synthesis was r arried out in the. same manner as in 1 Production Example 22, except that the composition shown in Table 3 was used, thereby obtaining water-dispersihle hydroxy containing acrylic resin water dispersions (M-2) Lo (211-5) Table 3 shows the composialon of raw materials (parts), solids content (fl, ac.t.cl value (rug KQH/g) and hydroxy value (rug KOH./g) 01: tthe water-dispersible hydroxy--containing acrylic resin water dispersions (Al-I) to (AL 5) In Table 3, methylene hisacrylemide and allyl methacrylate in the monomer emulsion for the core portion are polymerizable unsaurated monomers flaying two potyme.n.zaw.e unsaturated groups in one molecule. Further, styrene and 2-ethyihexyl acrylate in the monomer emulsion for the shell portion are hydrophobic polymerizable unsaturated monomers.
1.5 [Table 3]
a _________ _________________ ________ PruduronExarnre -21 3 24 25 26 Water dmperco of atr rb!e hdroxy-oontauiEng -A -2 A3 A4AI 5 Water 126 128. 26 128 128 EO2S_______ _ amnior.um pers&fata equnis okthon 5.3 1 s.3 aS -_2. _______________ f0sonxed W3rn 40 [SF1023 26 26 25 1 28 23 ethverebsaamide____ 21 21 NM rthryts ______ ______ _________ 2 1 2 Monome' ervuls3on to Acryamth 2,1 con, -....... , ____ - 2828 28 28 28 Methy metharyts -15.1 16,1 -161 -161 -161 -Ethy ntIt 28 _____ 28 29 28 ________________ ________--21 -21 -21 Oere1wate U U 11 17 SR-1025 1.2 1.2 1-2 ii --1.2 -Ammnp'sMate ___ 003 002 1103 003 003 Styrsne ______ ______ 3 -3 - Moronic, erwlsrcn for &L hecyi ayIt; -3 - 2-hyth-oxyrsthyl or4ate 51 5.1 5.1 ii] -5 1 5i 5 51 j-,_!Y_. b ______ _______ 9 [EthY 30*ts -iL,. J,L. iQ. 13 -0 9 9 9 -_ 5% Iiyirrh etbcno aqsQks-&ton 40 40 -40 40 40 Sohth content.30 JO 30 30 30 Aced vaS gKOEUg 13 33 33 33 33 Hydroej vdue t,nKOH/& 25 25 25 25 25 Further, in Table 3, among the water-dispersible hydroxy-containing acrylic resin water dispersions (Al-I) to (Al- 5), (Al-I) to (Al-3) correspond to a core-shell---type water- dispersible hydroxy-containing acrylic resin (Al'') -- -Production Exar Ic 27 --parts of propylene clycol monopropyl ether was placed into a reaction vessel equipped with a thennometer, a thennostat, a stirring device, a refiux condenser, a nitrogen gas introducing pipe, and a dropping funnel, and heated to 85°C.
Subsequently, a mixture comprising 30 parts of: methyl methacrylate, 23 parts of 2-ethyihexyl acrylate, 29 parts of n-butyl acrylate, 15 parts of 2-hydroxyethyI acrylate, -6 parts of *15 acryLic acid, IS parts of propylene glycol. m000propyl ethet, and 1 03' 2.3 parts of 2,2''azobls(2,4'dimethylvaleronitri1e) was added dropwise therer.o over 4 hours. After completion of the dropwise addition, the u.xture was aged for 1. hour. Subsequently, a mixture of 10 parts of propylene glycol monopropyl ether and I part of 2,2' azobis (2, 4dimethylva1eroni.tri.i.e) was further added dropwise thereto ocxer: I hour. After completion of the dropwise addition, the mixture was aged for 1 hour. 7.4 Darts of caethan*oannne was further addea thereto, noreby ootasnncj a hydroxy---contai.ning acrylic resin solution (A.-6) having a solids content of 55%. The obtained hydroxycontaining acrylic resin had an acid value of 47 mc; KOH/g, and a hydroxy value of 72. mg KOH/g.
Product ion of Hydraxycontaininq Production Example 28 109 parts of t.rimethyi.o.lpropane, 141. pacts of 1,6"-hexanediol, 126 parts of 1,2-cyolohexanedicarboxylic acid anhydr.i.de, and 120 tarts of ad.i.nic acid were placed into a reaction vessel equipped with a thermometer, a thermostat? a stirring device, a ref Lix condenser, a nitrogen gas introducing pipe, and a water separator. The mixture was heated to a range of 160°C to 230°C over 3 hours, followed by a condensation reaction at 230°C for 4 hours. Subsequently, to introduce a carhoxy group t.o the obtained condensation reaction product, 38.3 parts of trLrnellitic arihydride was added to the product, followed by a reaction at IiOC for 30 minutes. Thereafter, the product was diluted with 2ethyl---l--'hexanol (nwtss that dissolves in 100 g of wate at 20°C: 01 g), thereby obtaining a hydroxy-containing polyester resin solution U\2-1) having, a solids content. of 70%.
The obtained hydroxy-containing polyester resin had an acid value of 46 tag KC)FI/g, a hydroxy value of 150 rag &OH/g, and a number average molecular weiqnt of 1, 400. In the composition of raw materials, the total content of alicyclic polybasic acid in the acid component was 46 mol% based on the total amount of the acid component.
Production Example 29 113 parts of' imethyiolpropane, 131 parts of I u 4 rieoperityl glycol, 80 parts of I, 2-cyciohexanedicarboxylic acid anhydride, 93 parts of.i.sophthalic acid, and 91. parts of adipic acid were placed into a reaction vessel equipped with a thermometer, a thermostat, a stirring device, a.reflux ondener, a nitrogen gas introducing pipe, and a water separator. The mixture was heated to a range of 1.60°C to 230°Cover 3 hours, followed by a condensation reaction at 230°C for 4 hours.
Subsequently, to introduce a carboxy group to the obtained condensation reaction product, 33.5 parts of trimellitic anhydri.de was further added to the product., followed by a reaction at 17000 for 30 minutes. Thereafter, the product was diluted with 2-ethyHlhexanoi, thereby obtaining a hydroxy-containing polyester resin solution (A2-2) having a solids content of 70%. The obtained hydroxy-containing polyester resin had an acid value of 40 mg KOH/q, a hydroxy value of 161 mg KOH1g, and a number average molecular weight of 1,300. In the composition of raw materials, the total content ot alicyclic po.l.yhasic acid i.n the aci.d component was 28 mol% based on the total amount of the acid component.
Production Example 30 A hydroxy-containing polyester resin, solution (A2-3 was obtained in the seine manner as in Production Example 28, except that ethylene glycol monö-n--butyl ether (the mass that dissolves in 100 g of water at 20°C: infinite) was used as a dilution-solvent in plade of 2-ethy1l-hexanol.
Production Exarcpie 31 In a stirring and mixing container, 19 parts (solids content: 14 parts) of "GX-8 OA' (product name, manufactured by Asahi Kasei Metals, Ltd., aluminium pigment paste, aluminum content: 74%), 35 parts of 2-ethy]r--l-hexanol, B parts (solids content: 4 parts) of the phospnorc acid group-containing resin solution described below, and 0.2 parts of 2- (dimethylamino) ethanol were uniformly mixed, thereby obtaining an aluminium pigment dispersion (P-l)
-F
Phosphoric acid group--containing resin solution; a mixture solvent ci 27.5 parts of methoxypropanci and 2/.5 parts of isohutanol was placed into a reaction vessel equipped with a thermometer, a thermostat, a stirring device, a reflux condenser, a nitrogen gas introducing pipe, and a dropping funnel, and the mixture solven was heated to 1lOC. Subsequently, 121.5 parts of a mixture comprising 25 parts of-s*yrne, 27.5 parts of n-butyl raethacrylate, 20 parts of "isostearyl cry1ate" (product name, manufactured by Osaka Organ.i.c Chemical Industry, Ltd., branched higher alkyl acrylate), 75 parts of 4-hydroxybutyl acrylate, 15 parts of the phosphoric acid group-containing polymerizable monomer described below, 12.5 parts of 2-methacrvioyioxy ethyl acid phosphate, 10 parts of isobutanol, and 4 parts of t-hutyl peroxvcctanoate was added to the mixture solvent over 4 hours.
F-rther a mixture comprising 05 parts of t-hutyl peroxyoctanoate and 20 parts of isopropanol was added dropwise thereinto for 1 hour, followed by stirring for 1 hour for aging.
thereby obtaining a phosphoric acid group-containing resin solut.on having a sol.id.s content concentration. ofO% -The phosphoric acid group-containing resin had an acid value of 83 mg KOR/g, a hydroxy value of 29 mq KOH/g, and a weight average molecular weight of 10,000.
Phosphoric acid group-containing polymerizable monomer 57.5 parts of-monobutyl phosphate and -41 parts of isobutanol were placed into a reaction vessel equipped with a thermometer, a thermostat, a stirring device? a refiux condenser a nitrogen gas introducing pipe, and a dropping funnel. After the mixture was heated to 90C, 42.3 parts of glycidyl methacrylate was added dropwise thereinto over 2 hours, and further stirred for 1 hour for aging. Subsequently, 59 parts of isopropanol was added thereto, thereby obtaining a phosphoric acid group---containing polymerizable monomer solution having a solids content concentration of 50%. The obtained monomer had an acid value of 285 mg KOH/g.
Production Example 32 An aluminium pigment dispersion 19-2) was obtained in the same manner: as in Production Example 3]., except that 35 parts of ethylene glycol mono-n--hutyl ether was used in place of 35 parts or 2-ethyi--i--hexanoi
Example 26
Added to a stirring and mixing container were: 100 parts (solids content: 30 parts) of the water-dispersible hydroxy-containing acrylic, resin water dispersion (Al-i) obtained in Production Exarrp].e 22; .8 parts (solids content: 10 parts) of the hydroxy-containing acrylic resin solution (Al-6) obtained in Production Example 27; 43 parts (solids content: 30 parts) of the hydroxy-containing polyester resin solution (A2---l) obtained in Production Example 28; 62 parts of the aluminium pigment dispersion (P-i) obtained in Production Examr'.le 31.; and 50 parts (bolids content: 30 parts) of the melaxuine resin (B-I) (methyl-butyl mixed etherified rnelamthe resin; the solids content is 60%, the weight average molecular weight is 2, 000) ; and the mixture was uniformly mixed. Further, 5 parts (solids content: 1 part) of the diluted j:l.uid ci:copoiyner (RC-l) obtained in Example., 2- (di.methy].ami.no) ethanol, and deionized water were added to the mixture, thereby obtaining an aqueous coating composition (X-l) having a pH of 80 and a solids content 01 25%.
Further, as for the obtained aqueous coating composition (X-i) * a xiscosity V1 at a rate of shear of 1, 000 seC 1 and a viscosity V2 at a rate of shear of 01 sec, when the rat.e of shear was varied from 0000l secT' to 101000 seC', were measured using a "HAAKE Rheostress RS150" (product name, manufactured by H.AAKE) viscoelasticity meter at a measurement temperature of 2.0C.
Examples 27 to 57 and Comparative Examples 6 to 12 Aqueous coating compositions (X-2) to (X-3) having a pu of 8.0 and a solids content of 25% were obtained in the same mariner as in Example 26, except that the formulation composition shown in Table I was used- -1O7--
[Table 4]
T8be 4-1 __________________________ _______ _______________________________________ ExsrpFo ;r' --r 26 2. aiaao 31a2 33 34.35 Asooss *oMA;1 co;npo&.*0 X-l X-2 X-3 X-4 X-5 -o)-7 x-8 x-s x-l0
-------
Water dsorskn of gator-1vpersñ s 110 00 300 leO l)fl ilydry-000ta;nFn8.
* . oryhc resoi (Al-li (Al) Hydroxy-oonSrng.
resn A is is 18 33 19 W l 133 13 iS n.sfr solstion (6,1 --6) . HYtar 43 43 4 83 43 F 43 43 43 p&ycstor * (A2) rosm so:ut,on.A2-1. . ------t-÷--Cngagsot(B) Melsmh,erSn(B-i) 50 50 50 50 50 50 50 50 50 50
--
P1 01 PILF1 P1Pi p P lfi P A3urnsi;srn p,gment sperson "-----.
_____ CrtFt _____ 82 02 62 3262:62 o2 02)82 02: -. TYFe 80-i 80-2 0-3 jRGRC R0-7 cc-s ROt Otsdflu4otoopo?ymer ________________ -.* __________________ Ouanttv 5 6 5 5 5 5 5 5 5 5 %flsuoatv V, at s rats of Srnsr.f lOaoil'[Ps-sso] 0.05. W)S 6.05 0.04 0.04 004 01)4 0.05W ti.081 0.055 ____ ---.-.--------.--.-----. 4 Vsoosty V fl a rate of shear o 0.laso'[Pe--aac] 48 43 38 35 32 35 55 59 55 1000 900 950 F 8Th 800 000 882 887 IOCO ta5k 42 &LqJaaANtL as.
Aooeoua coatingcospositicn X--33 X-12. X-13 X-14. X--i5 X--i5X-i7.X--Ut X-l9)P14) of HVO FossrsbEe h,droxnnorg 3(10 100 130 100 100 100 100 100 100 103 O1F1l58 laCfl.SO ts fl (A 1) 8oyln.rsar r-----------m------F-4or. Ing rosy-cort:rirg o-yhc 18 *8 10 18 iS 8 18 18 *rA) s-----------------4'------. -1.
,nb r.n ly*csrcorts rnnjt,yeste 4 1 43 4)3 & 43 43 raa,t:t*Oifl 3OLtOn (Ak1 (A2) ____________ 56 50 50 gQ 5(3 10 50 50 50 CL:rinf (B) IEsrnna ro& (8-2) t4) . . . lype P P1P-1 P-I P-i 03 P1 °1 NI PH AiypnLrnpcment thspsrwn Qu,nty ---w w 82 icr i irfir I 80-80-80-. 80-80-80-RN 80-RN 80-Oi5itediuid of ospolymar WO 33 34 15 16 37 15.
____________ 0jntrv ____ 5 5 515 S 5 5 5 5 5 -. -. -. --4---Vsoo ty V at a r330 of shoar of iO)saC'[P-tec 007 O0 6 C 005 005 oo oo; oos oco f -t--, so [Pa aso 50 501 50 46 42 50 50 5050 VjV 714. 7141 7141 9001 840 714 71 -.--...-..--.-.-.---.-----.-.-.-.-.-... &tu
COt!fl;flZ *C(CF!Sfl 390.100 100 00. ;UO (Al -1) ..
W!=' iQp8r$fl 0 v tr-3oorio ythcixy-. t*"tl:fl;fl3 acryhz rsr, . 4 ____________ --I---.-Wcke, nrs,ncif torenNci hvcl,c.xr.
* ct2n;r4 scr4c, 4 117 * *
-
A o te, per 373. cc! o c wcl 00 (A) A1-4) j * Wat*r 41sOgr8ác 0 watr-ofts *sy: *nSg rcrin 100 --IT 1 [z $** 43 43 43 4 4 43 43 3 43 50 30 511 50 50* 511 50 504 v e 3?34thn V' !23111 0' ---1 P-i -3 -i 1>-P3 P 4' 9' c i 22 23 24 11 l 4 319-90-.
a b 5 t 5 5 4i_4.
Y at rO) of 3,ora' i00Ogc iPr so 005 04114 oo3 011311107 SinS OQ4 34:37 4 43 44 1 3! fs iaitw 1 ____ -. -Go paret o e 117 b I 8 9 0 It Aoimoos coatinoornpostioo K--al X--32 X33) X--34X--35 X-26 X--37 X--3EHX--$).
-1------tWater eps,on *t wagrd:pers;bln hydrcy-contshOg 4c n,srt tOO 1110 lOU 100 100 lOU IOU 00 1)0 1 (A1 I -oita;ngatryit I-----------------------------.----. -----------.---.---- rs)n (At) . -- Hydrosoontnrngaoryho -sotjtar, (Al-ti reair () ydroxy--conti;st;g pOyd..e' 43 43 43 43 4 ecoktsontAz-flv I-tyd,r-,rrthtning pSyaster -. o&yester r*', it&o aot,stion (A2-2) CAl) -Eydroxy--containir! polyootv 43 rthi sok4icr (fl---3) Cirn agrt (8) MSarnk,a rsth, (Pt) 9 50 00 50 iSO 00 50 50 50 ASrv:rnnpigmecso'ave "" Qwantst, -62 82 92 82 82 82 82 82 92 * . --RO-IlC-2.RC-2 26 27 29 2' 30 fkid of copoIynir : --Qtanttty 5'5 S-S 5 55 Vioaothty-cenboElin agent ACRYSOL RM-825 (*5) 1. .
-
Vso*1ty V ata rate of shear iii n1(tOae--[Pa--seo} 0,0-) 0.04 002 *O(] 0.03 Q05.0.03 aoi 0.92 VosttqVa?t 1 20 5 5 iI EJE I (Note 4) ?4eiauu.ue resin (B-2) methyl etherified melatnine resin; the solids content is 80%; the weight average molecular weight is 800.
(Note 5) "Bayhydur VP L&-2310": product name, manufactured by Sumitomo Bayer Urethane Co. Ltd. * blocked' polyisocyanate compound; the solids content is 38%.
(Note 8) "ACRYSOL RM-825" product nsme, manufactured by Rohm and Hess Company, urethane-associated thickener; the solids content is 25%.
Production Example 33 A thermosetting epoxy resin cationic electrodeposition coating composition (product name "Electron GT-l0", manufactured by Kansai Paint Co., Ltd.) was applied by electrodeposition to a zinc phosphate-treated cold-rolled stes I plate (30 cm 45 cm) to ---110--* elm thickness of 20 pin, and cured by heating at 170°C for 30 minutes. Subsequently, an intermediate coating composItion (product name TP-652, manufactured by Kansa.i Paint Co, Ltth a poiester resin/amino resin organic solvent--type coating S composition) was applied to this eJ.ectrodeposition coating film to a film thickness of: 15 pm, and cured by heating at 140°C for minutes Thereby, a substrate comprising a steel plate and an electrodeposition coating film and an intermediate coating film formed on the.tee1 plate was repared.
Nethod of Forming Coating Films
Example 58 -
A multi.l.ayer coat nq film comprising a base coa.t and a cleat coat on a substrate was formed by using the aqueous coating composition (K--i) obtained in Example 22 as a coating material.
for fanning a base coat in the two-coat one-bake method in method I of forming coating films.
Specifically, the aqueous coating composition (X-l) was applied to the substrate obtained in Production Example 33 to a film thickness of lSpm using a rotary atomization-type hell- 21) shaped coating device, then allowed to stand. for 2 minutes, and preheated at 80°C for 3 minutes. Subsequently, an acrylic resin organic solvent.-based top clear coating composition (product name Magicron KIN3l210R, manufactured by Kansai Paint Co., Ltd.) was applied to the uncured coated surface to a film thickness of 40 pm. men allowed to stand for 7 minutes, and heated at 140°L, for minutes to simultaneously cure both coating films. Thereby, a test panel consisting of a substrate arid a ruulti.layer coating film comprising a base coat and a clear coat formed bn the substrate was obtainech 0 Examples 59 to 89 and Comparative Examples 13 to 19 Test panels of Examples 59 to 89 and Comparative Examples 13 to 19 were obtained in the sante manner as in Example 58, except that the aqueous base coating compositions shown in Table 5 were used in place of the aqueous coating composition (K---1).
-i_I 1.-Evaluation Teat I Each test panel obtained in Examples 58 to 89 and Comparative Examples 13 to 19 was tested for DCI, flip-flop property, metallic mottling, arid The test methods re as follows: DOl: DCI was evaluated for each test panel based on the Short Wave (SW) values measured by Wave Scan" (product name, manufactured by ElK Gardner) The smaller the Short Wave (SW) value, the higher DCI on the coated surface.
1.0 flip-flop property: Earth test panel was observed visually from various angles, and the flip-flop property was rat:ed according to the following criteria.
A: Variation of the brightness depending on the angi.e of viewing is sian ificantly high (extremely excellent flip-flop property) 8: Variation of the hri.ghtness depending on the anale of viewing is high (excellent flip-flop property).
C: Variation of the brightness depending on the angi.e of viewing is slightly low (slightly poor flip-flop property) -I): Variation of the brightness depending on the angle of viewing is low (poor flip-flop property) Metallic mottling: Each test panel was visually observed, and the degree of occurrence of metallic mottling was evaluated according to the following criteria: A: Substantially no metallic mottling was observed, and the coatIng film has an extremely excellent appearance.
E:Asma Ii amount of metallic mottling was observed, but the coated film has an-xc1lrit appearance C: Metallic mottling was observed, and the coating film has a slightly poor appearanceS - 0: A considerable amount of metallic mottling was observed, and the coating film has a poor appearance.
Water resistance: Each test panel was immersed in 40°C warm water for 210 hours, then removed and dried at 20°C i:or 12 hours Subsequenr±y, cross-cuts reaching the substrate were made In tb-c mulila-yer coating film on the test panel using a cutter knife to form a grid of 100 squares (2 nun x 2 mm) Afterwards, an adhesive cellophane tape was applied to the surface of the grid portiOn, and abruptly peeled off at 2000. ¶1?he condition of the remaining coating film squares was then checkecL The water resistance was evaluated according to the following criteria: A: 100 squares remained, and no edge chipping occurred.
0: 100 squares remained, hut edge chipping occurred.
0: 90 to 99 squares remained.
D: The number of remaining squares was 89 or less.
10. Comprehensive Evaluation
For coating vehicles and the like in the field to
which the present invention pertains, all of Dcx, flip-flop property, metallic mottling, and water resistance are expected to be excellent.. Accordingly, the comprehensive evaluation was conducted according to the following criteria: A: 001 ((SW) value) is 12 or lower, and all of the flip-flop property, metallic mottling, nd water resistance are A. B: 001 ((SW) value) is 12 or lower, and each of the flip-flop property1 metallic mottling, and waLer resistance is either A or B, with at least one of them being B, 0: 001 ((SW) value) is 12 or lower, and each of the flip-flop property, metallic mottling, and water resistance is A B or C, with at least one of them beIng C. 0: 001 ((SW) value) is 13 or higher, or at least one of the flip-flop property, metallic mottling, and water resistance is 0.
Table 5 shows the test results of the coating film performance
[Table 5]
Thbe 5 __________ .-._w______ -t-r-----{ Luer Aquous ---Thter Ccanprehonswe oa..'ng: DO:Fp--flop Mato$c resisPince evuton cnnpcss:ton:prope(ty rnotUing r rrr r-r r- 59 X-2 7 A A A A X-3 6 A AjA A 61 X-4 9 TA A A A 62 X-5 9 A A A A 63 X-6 0 A A A A #4 X-7 9 A A A A X-8 9 A A A A X-9 9 A A A A :67 X-lO 9 A A A A 6 X-11 9 A S S 69 X-1? 9 A X-43 9 A A S Ii X--H 9 A i A A A 72 X5 9 A A A ft 74 X:Th 9 A B Exampe _____ _______________ __EHE± _ -Ia Cepretiee Exmpk 16 X-36 17 C C A 0 0 9 X-6 C C A 0 _._._ fl X-39 30 C C-A 0 cL-c Exaxppies 90 to 120 and Comparative Examples 20 to 24 S Synthesis was carried out in the same manner as in Example 1, except that the composition shown in Table 6 was used, thereby obtaining diluted fluids of coooivmer (RO--Ji) to (RC---66) having a soitds content of 20%.
Table 6 below shows the composition of raw materials (parts and weight, average molecular weight o.f the diluted fluids of copolymer (RC-31) to (Rc-66) liable 4] Tthk 6--i ____ ____ i] 42141 95 997 99 DedFldoCoar tWN 39 I rw I I ryt 1 m I m 1 tm 1 fin" ?fl"1" I 2 3 4 qk" ) wtLon 3,-. ,, ,,,,,,,, 154 154 154 354 71 1b4 I54 1b4 164 15 Potwi n4i antur4ed Cwn:*ont(m) wxnomer 9rg Ae-v3,o o a 2/ 2' 27 21.195 2/ 225 30 32 4 hydrh/a group
__________ _________ I
Ft/ycirrt 63 63 63 61 965 63 67Z3 60 58 54 Perbut*O 015?fljjIfl 0l5 Conthrto'mnron,onomer(rr-3 EMs% 10 10 10 10 5 ID 10 0 10 & 19 ons*tirtS monr tnv g Z' ç7' ;T 29 27 225 30 32 16 conthrt of thor poEyrnoriabe unoatw-aed aonocnerv G,r-3) L'Mas, : . .1 " M ;; mthrweht(wi01 __ j33034 so s E*b!e 6-2 _____________________________________________ _____ ICC 83:j 834 8350O1 Td
--
RC-RU-RU-RU-RU-RU-RU-RU-R(>-Duth F:tnd ot Cnooiyrnar 41 42 43 44 45 6 47 49 49 50
___----_
-a--l--jrn-l- ntnfrcwk -in-3-rn---bI 3&au-onnnnrrer(m-31 12 32 1 3 a a z 2 scRit-on -------------,------t---------I -___ 4tj 164 454154 154 th4 354 fl4 154 Wi Aor'3acic3 21 aS 1 2.5 54 53 22.3 30 3Makbac."k t1d 27 I---r Mnontr Pa yro*rcabN s sattrtsd --____. - (ro) -moaorflar a L t-;m; 3-san2-rroiiont. 4 tlK-c'-erAMIUC I proW-Ivthyrnthttnflt1 iii -fl- snestwzt norjss Cm---a) EthyscU4az 635454 63 47 46 30 (tm tmc emta txceaL >>,asa azas 315315 8831015 835 835 015 OIShflS OnntentafmanvrwnrCrir12[Masfl] 2. JL.i1L iliji J!L J2 J&. J2..LJ.
Cnntent of uer3zaWe uriestsratad roonan,er having a hy*aoh3io Cm-.,. 34 2) 4aes%j ________ Cortrrtaf athcu eo manzable atr*t minnrors trr3Mass%j Fl J84 54 32 97 33(1 36 2' 34 tl Wstht ar rn&acua w.'bt LX 30" 38 Jao i!. L9_ I -Tab3e P'r3 ________________________ 111 1 1
-----
)3Se -3u 3 of Copobm,er 1C RU RU RC e
--
Macramonomer(m-IYP' 23 3 314 3 3 3 3 3)snk4ion _ ________ 4 C95 536 154 134 Perntr,atà derfleaci-335 14 34 38 29 j225 29 27 27 27 Monomer t<n'$ --------t,arnponent cml i aar hevng a $ fwdrox4oth3,erata P Ldnp**rg,-oup --33 5 btha a3a*s$ale 16 - * ____ * --; *63 QQQXtt-r&&---- -- 43S 815 015 815 8153015 2 05 0 2 Gontent. -,f i&y" eiieabk unsetunted monomor a jdtopi4m 10 4 18 2? 21 27 9/ 4Yfl!tfl (m-2) [Mass j Conten a other ooMnerrabo jn133Jrat4d moncrnefs cm-3 Ii#ses 18 1 82 74 53 525 36 53 53 83 ae3tav,rs3O rIO3OCVSF 2E4t[;t0'] -________ 24 1 23 20 20 8 12 38 li6-Table 13-4 _________ __________________________ Exarnle Con,paratve Enpe 0 0TJ22Th 24 n' n nfl nr nfl {Xld fl& flL 1.' fl Dthdd;dofCop&vmor BC-H rn-i-rn-i--rn--i--Mrrrnn Pt rr-t-3 i) ------------------------ 131 t54 $ 154 PoIynnN Arv. u4 7 71 0 77 21 uttreted -rng3nrnler H Morrner Componnt (rn) Methoth& ar- ______ _________ _______ _______ L. --015 0.15 015 0i 0.15 Conte,it of rnacronionomer (rn-i) (Mess % 10 --10 0 10 10 0 Content of ç,oyrne-nth trnsaturated onrner hev,r,g 21 27 27 20 l;dmphIc grtu (rn-2, [Maes.
Cesnent of other pol,,rnerzable trs,Aurathd rnonornors (rn-3) 63 63 0 NthJ,t werege molecular w&ght [x104] : 42 20 30 28 j-31 30 (Note 2) NK-ester AN-90G": same as described above (Note 3) "EE:EX 6954--C": same as described above.
ProducLionofAqieousCoatinq_Compsition Examples 121 to 158 and Comparative Examples 25 to 31 Aqueous coating compositions (X--40) to (X-84) having a pH of 80 and a solids conLent of 25% were obtained in the sane manner as in Example 26, except that the formulation composition shown in Table I was used.
[Table 1] -
Thbh 7-1 Exerrpe 21 122 123 124 125 126 121 126 129 130 _________ Aquais OorUng_Corpoaiticn X-1O X-41fX--42: X-42 X-.44 X-45:X46 X47 X46 X49 er&onof H dr p 100 1 100 100 iOO 100 100 100 100 lOG 300 Y OX) hyorc,xy-containing 3
OP -
acrylpc rsapn ---Hydroxy-oritatrnng F4nt1orrnog arar5o 18 18 18 lB 18 18 18 16 16 18 (p,) reso sc1t,tcn (AN6) I Hydrow-- :lvdroxy--ctnn9 -polyaster 43 43 43 43 13 43 43 43 13 43 polyester,es,n A2) res*r, sok*,qp, (Act CusngagtCB)4ar,eresm(B1' 53 50'St3 50 J50 50 50 50 50 ---type P1*P1.Ni P1P4Pi P-I P4 Pi P1 Ah,n,nun pPgrpss t d seton §2 62 62 62b2 82 62 62 32 82 RC-RC-RO-RC-LRO--RO-PC-PC-Rb-PC-O Thsd of cop&ymer 31 32 33 3435 3 31 38 38 40 * Quaty 5 iS 15 iS 5 15 iS 5 -15 Th Vscothty V1 at a rate of shear of l000se6'[pa-secj aoo 0.05 0.05 0.04 004 0.04 0.04 056 0M61 0.035 V,t t,aty V at a rate of shea, of 0 lsec Pa-seci J 4' 42 fl 33 30 fl bI 55 3 744 930 837 881 814 744 831 913 900 930 Table 7-2__________________________________ ___________________________
Example
__ a a fla Apvevus Cost;r; Cornposkio X-50 X-51 X--o2 X-58 X--54 X--SS I X-50 X-51, *-53 I * -----later disparscn of water--li,ereible wo ioo F 100 100 100, 1001 100 100 300 101) nyc1rocr-contanrng I 34kxooc0s5r't s.ryl c re-cr Al-1) 4eresin(A1) -HydraMy-ccr:ta!rlccg -acrylIc 18 lB E 18 8 8 8 18 18 19 (A) real,, aoh;tion (Al-6) I lyjroxy ° polyester 43 43 43 43 43 43 43 43 41 43 p7sfle.r resIn (*2, rasin sottior, (2--I _______ ______-Mthrwo-eon(E--' so' íè' èiIW ii Cunn, ent B brfbrtb02) lyps P1 --3 P-I -1 P-i P1 I-3 P3 P3 P1 OSOtI anIon ---------------0-7 i i ii i PC OC P PC C PC PC PC R" PC Och'r31 liitsdoropol,,rnor 43 42 43 44 45 46 41 48 19 50 7' 75 75 75 75 7 7 75 7r Viscosit1V, at a rats of shear of i000seclPa-sncl 001 007 001 0.05 -0043 0.043)043 o04v: 0.07 005 Jemry V at a rats of shea' of 0 sec [Pe-ec] 41 "7 47 40 30 30 30 30 47 a'7 V,1V, 664 864 t$4 dUO 692 692 69 692 34 93 hk 3 ___________ r ds,erton of LOt 00 133 lao fl no no on -I: * s A 1 weores:n(A) U UtUig flrn-frrn:ngreai; 1l 18 UI UI 15 fl UI 18 18 16 I (A) -resin a&ution (M--iI) Hydry-vorl*oinn8 tHvdrojrcorrtarinm o*eater -43 43 43 43 43 4_I 43 43 43 43 ro a A2 rLan oIotoc, (fl 11 P-lPH P-I P-i P-s P-tP--LH'--l P-I P3I AUfl ient dia3rGn, tt -." 62 62 62t!62 62 62 RC--RC--FU>--EC--PC--FiD-PC--1Ra-G-C-- 4dofcspmer iL! t. ± ________________________________ 757.5 15 15-15 7.5J7Z17S 7.0-7.5.
V at a i-sb, of sh,*r of 0G0o'1Pa-anc] 0.115 0-08 0.08 0.08: O6 0O8 008 0.04 0.043 0.06.
V rat: rat: of th:nr of 0 2? 28 2? fT J7 2 C3 1Ok 7-4 ____________________________ _____________ - 4mpa * 1,7 b 1! r)-t, D *7 $*72 X Y *i,3 ( t --..------ !Wetr,rsin A -;ttr-. byciroxr I 30 ntacn;n,uc!;c ros1 P rnnt *ter hlspws;ai, ko'ce--tainE N,rylk rc:n Wtr kspr on of --perWe hv1n?rr-01 ynroxy-crrt.iMn *? rJfl Zyb fl op6o,e;,CA3) L______.___.. -.------_-_ c5qxrnfto, ,,f 433o6vbk.
J4f txoft F;ctorcctcc. -.. I: ___________ of natr.
-
jf4vzfrorrccrtaruiEezrfo. . p fi:43 43. 43.43. 4_% .. . 43 p >6 bO 43 -U" y&rVPLS4P(+n) 44 PU-F4G-PC 0 P0 Ai>-PC-PC .-----1LiLaa-asL!2.. P-63 P0--OS 7% .3% 7$ .6 7.5 7% 75 75 75 3.5 /nit' "i 04 of of Oc1Pno] 607 (5 p% :?54 004 004 504$ jo-i o.o * 82 I L _________________________________________________________ 843 853 8 8 33 7fl 453 35' 253 273 Tabe 75 ________ ________
Co mparabve. Example
27 26 29 30 31 Aqueous_Coating Corn sftion X-80 X--8i X-82 X-33 X-}34 * Water dispersion of water- Hydroxy--dispcrshle hydroxy- * oontanhig containing acrvEuc resin eslru I (Al) Hydroxy-sontaincig rylio Fdni-formung resin resin soiution (A1-6) (A) Hydro-- -Hydroxy-containung corainung polyester 43 43 4-3 43 43 polyester resin..
(A2) resin so:uton A2---1) Cunng ant (B) MSamcne reBD 50 60 50 50 50 -Type P-I P--i P-i P-i Ni 4iurninium grnnntthspersion f 62 62 62 62 Diluted fluid of aopolymer Type 64 ____ Quantty _____ 75 75 75 ____ Vuscosuty-eontrothng agent ACRYSOL RM-825 (tB) 6 Viscosity V1 at a rate of shear of i000se6[Pa-sec] 0.03 0.05 0.04. O5 0.02
-
Viscosity V2 at a rate of shear of 0.1sec[Pa--sed 14 18 13 1 I
--
___________ ____________ 465 7j45Jj40 50 (Note 4) Melarnine resin (B-2): same as described above.
(Note 5) "Bayhydur VFLS23l0 same as described above.
(Note 6) "kRYSOL PM--825": same S described above.
Me thod of.FonuingJ9 tine Films Examples 159 to 196 and ComparaLive Examples 32 to 38 Test panels of Examples 159 to 196 and Comparative Examples 32 to 38 were obtained in the same manner as in Example 58, except that the aqueous coating composition shown in Table $ was used in place of the aqueous coating composition (X-1).
Evaluation Test 2 Each. test pane.1 obtained ifl the Examples i.59 to 1% and Comparative Examples:32 to 3$ was tested for DCI, flip-flop property, metallic mottling, End water resistance, and these properties were comprehensively evaluated. Each test method is as described in the Evaluation Test 1.
Tble shows the. test: resuits of the coatinc4' film perfonnance.
S [Table i*
Tthils Lszfler Aot,eous ccSIR 1 Wtor Comprohonivo composition 0O ThPtP Metathe rsstnos vauatirni I; c flL A EE a........ a_, &_ &_.
X-44 10 A A A A V5445flAAAAi H65 X-46 10 A A A A Th9 X-47 10 1 A A -A Al L__ _t:_ 168 (-49 10 A A A A X41 10.3 A A B 111 X-52 -10 B -A A B 172 X-53 11 A A A A 173 -10 A A A A 174 X55 10 -A A A A Example --A --A B B Th TC Th UI X rio __ 178 X-59 8 -A A A A 19 X-âO 8 A A B B XflB_rA A B X-62 10 A A B X-tA 9 B A A B ,-.-- 103 *14 10 AJ A A --10 A A B 11 B -A A B 186 X--O7 11 B B A -6 x-43 10 A A A A - :B 191 X--72 10 A B -A B X-71 193 X-74 B -B -B B 194 X75 12 13 j3 B B ± rLC TC _________________ 19 X-1 0 B A B D 0 A 0 33 X-79 28 0 0 A 0 1 x-o Cnparathea Exe4mpie 35 38 0 0 A 0 X--82 I? -T ci c -A] 0 37 X43 0 0 A 30 0 0 A 0 otj9plymer Examples 197 to 228 and Comparative Examples 39 to 43 Synthesis was carried out in the seine manner as in Example l except that the composition shown in Table 9 below was used thereby obtaining diluted fluids of copolymer (RC-67) to (RC-103) having a solids content; of 20%.
Table 9 below shows the composition of raw materials (carts) and weight average molecular weight of the diluted fluids of copo±ymer (RC-67) to P&t03)
[Table 9] 8-i rampk
______________________________________________ 197i8 199 200., 201 I2i.21 204 ns tR2 Pq S$S S.JL 2L.21:iL Jq7 -fr rn 1-sr-ni-F--t-n-I-*n-1--rr-i rn-I Mroronouerv (1 4 r 8 78 9j10 t -. --i± Monomar N 35 315 35 33 35 Conpornt cm) rrnzthrtzd t4oted ---t:: Zrn;de.-1eqp vprrra± 313 1I 36 33 3I 5 16 18 Cm-2) »=--hydro:crathy nvte 27 27 27 28 27 27 27 27 27 PS,ttyf-O 015 015 015 01b015 015 015 t.15 01 Content frnromonornr(m-g) [Mass %1 0 W 0 5 1 * 9 1 10 rw(r2tMssI d J______ Content f oth p&ymerü&o un turned yr 9S Cm-a) [Ma 0 0 0 9 F o a a 0 w?isht verg r uktJar &tht [,ci04 31 31 31,,:__ ___ _--- -i23-fa8it 8Z __________________________________________________________________________ ________________________ --. I. cCj.5Cjzc ii * TRC-O-3fi0-3R0-1RC_rrtflC_hURC_ ----wcdfu,2o oo.nsc [5 Ir 03 fl 1.3184 S 15 37 o -. f-j f "4"r rr3ri-'sri t, jn.1*3m.l'u' c* tnccc eiuto-' < __4j2t33S 1520113 333.5 I 54'5.4S435.* ,4115.41:SAISS.431b.4 15.4 1&4 55.4 S.4 i 5 I 21 25.51, .14 II -1 --4 - 5'ce1-,s,yrbIa eo, rnzabbe M*nnw swznt a,.hratcI unest.ned moctoic. k ccter 434-5(53 1 (p'} -flOfl'.. 313'drg 3 hecI-s s pa3yc,e vIar c.Nz ff41) 51.50 50 27117127 17 V 72 ____ -I + 1 3 15 ;:r s., :i L: LI:: JI.:. : :. .:.:1:.: ::1.:i:..::..:: --1----4--- S ktH3. OJO 304 SiS VS 075 015 0151075 055 015 19JJi 24Ja if. S. ocr2] , go 2 2; nrltonttQ.e 0,'en.Issb3nttnQ1orlcstr3)ft4sV 3 0 0 0 8 C 0 0 0 5 83 4b 2 o:gttwroger.Si wox10l Ii 31 1 s. LL!2 t IJL Tth1s 9-3 _____________ 219 220 221 2221223 224 225 226 227
-_ -
RC-IL-IL-RC-IL-3W-.RC-IL-3W-rkted fluId of copolyrner 3: sn-it rN nrl' nrltccrI-' csrl-'nr-l 5-fl3.
rQPI000t100r (nrl.5 Type 2 2 2 UI 3.
3 Qoserltlt/ 154 L14 354 271 3$ 3 4 154 154 N N-dothysormgde Jto 435 585 287 46 315 315 43 Po3y1nrah3e sThfttths -* --Monomer N-Iscpropyo3amIde 38 281 26 315 315 315 Cocrponent m) hyrlropMlo -27 -;; ;; 27 grolIri krn-2) AoryEo cold 28 43 5 29 Othmrpom sable I..i,: unoatorated monomers Ethy3 asrybte 35 * ----_-t-. -sobtVfl1eth!ej_ Pem±rO __________________________ 035 6l5035 0E5 0151035 200 050 032 5-.-Cooterltofrnacrum000mer (rn-i) L'Mess % ___________ 30 0 30 38 25 35 30 10 30 Coctert of p ymsozeble is ttaretad ow crow hevm1⁄2; hythop co <.
grosip ut-2) iMeso %] Content of other poIyrcIesizeb3e tnsatlnatod rnoncooers (m-3) (Mass %J 0 0 5 -0 0 38 0 0 0 Wet,t eVeFcpXe ID&eCO381 weE?M [<ioi 19.. L.1L IL 22. L. 3' 38 l24 Thbit, 9-4 _______________________________________ CcrvparMive Esrnp3e i'u4 of eopoy nr PC93 ¶., M: I Oi Mcrononorn ( sotr 5 IS t 4 154 e e$(rneth) ctrc thèt od l 5 31 5 35 515 11 [ 4to4-Se 31.5 31E 35 31.51 33.5 Pdymcrizth; PmerrsbI Monooar C:r.poncsnt upatj,aeI (m) q,ona,r *ng I fl S'$ -U ("3) yoronh he flUP,yozHay one e1aqn nr2) Jny-t pro done thY eth.1 ao-tu 21 2, 30 thactyho ollid. . 20 pc,rng ptle ________ --f 30 3 010 fl15 OSS 015 015 of,neoroyonorow(nrl M! . . .. H) -;rl Cc,tter* of 1rntnmbb jns,tomtje tonnn'er havtn, fr-sd e,h] r gre c (i,t-2; %j 0 100 50 50 CC lCe,tent ot other polvmer&abe urtsetw'athd morternere (cm-4) [Ms %) 0 0 0 0 0 40 it avtrge minuEr w&ght ExlOl 42 31 31 fl 31 31 1 (Note 2) "NK-ester AM---90G': same as described above, (Note 3) "FLEX 6954-0": same as described above.
Production Examples 34 to 47 Synthesis was carried out in the same manner as in Production Example 22, except that the composition shown in Table below was used, thereby obtaining waterdispersible acrylic resin water dispersions (Al-'7) to (AJ.-20) Table 10 shows the composition of raw materials (parts), solids content.*(%), acid value (mg KOK/g) and hydroxy value (mg KOH/g) of the water-dispersible acrylic resin water dispersions (Al I) to (l-20) Is -[able 10] F-r -___ ProdLta Exzmpi IJL 2LJ Waer di&pr&or of watr--d porthe EioryRc refli.. I. . AI-:.7. All A1-9 Ai--i0. A1tI A1-12 A1-13
__ -
water. .JL. . 40 40 40 Ajekeno So%»= SR-lCS 28 28 28 3 At 28 28 2 2 2 2 PoFyrnerixthk uti tunteci rnotoner hevW -L wo or r,or po yii zebEa Lsatuntod Methyknieb s aGysmde ______ -2 roup per molEcule -t-t---- ____ MM met1wcfl?o 11 -3 ____ Monorn:r amilsion kr cc, e Fthophobi Mosonier Component (b) I Pymcsthle poynrzthe -&t ecrycte 0 S 10 10 10 10 47 unseturted juetrntd monomer monornerha*.g zJi_.____..__-.. -.
one pcirrsr;abie Polrermbe rthr4et 54 55 52 52 48 52 22 uneetur&ted group reetureted monomer ______________ pe noeoue hs-ng C or C2eky j'Eth, ecryste 11 iS 12 12 2 12 5
-F
Dcred,ete, . I? 1 i: 17 1? . U. 11 1' . _______ Ade1cerSoerS4-025 12 12 F 12 2 12 12 2
_ --
_____ _____ -nnste 003 003 003 004 F 3 3 3 -ydrophor &yrre hk Qc--turlted 2CEth _______ 3 4 ii II 1 ii 15 monomer (b-i) __ - *-:---t-----f2-ethyihextacr4atc ________ 3 ____ 3 Monomer elmO don 1⁄4d she Hydrxy-oont3nFn& pc yrnerizable 2-ny*yethyl 2 2 2 2 4 2 J 2 unsetursed lorofrFsr (o-)) melhcrvlet _______ _______ _______ Moionsr Ccmponent (b) *Aethecry c octd 2 2 2 2 4 2 2 unsetureted monomer cr3- +-.--.-----,----r 1 abe PjFmerebie Mefty rmethiylate P 0 4 4 4 4 1 cd, C Z usaturatSr monomer -----.
mnnnornr,r Ur4, havug a l 5r tj2 alky Etht ecryats S 5 1 1 1 ___ --= fl - % ethenoi eoution 40 40. 40 40 40 40 40 Prdueton xomp!e ___________________________ 34 35 36 37 JO 39 U tjotsr thcpe;rn of ws or dspersb a scryho rerpn Al-i At-s A1-9 tI-iS Al-li Al 12 Al 3
--
,moJ t o pJ-enzgbFerp-a4urated monomers (arroLr of mono et. component b'} (parts] 100 1 Ji iOU 1QO 100 100 00 jjTmotoTccrmng monomer ocimpw ents (partsl 77 7 1 77 Si Ta al amomt of she F orrung mcncmsr ooapOrents 4 3 23 2% 23 27 23 23 fr4raphoboedymsthabie isatjratadrüràmai 1 24 24 24 124 -65 (b-i) _____ _____ HydroySirn p yweriaWe unsaturated 2 - 4 2 2 rninorrner (b-2) _______ -Conent of aed mororrer (mass %] besS on ftc total amt-u a p&gmerablcs unset-rot5 morrjrrer (amount of nor amer Ca barr COnEnEn1 poyniarizab a ui ureted 2 2 2 2 4 2 2 monomer (b1! PoiymerkthS urpttedmbnthrnor (b-4) ethr -then the pcymeraabk unsaturated monomers (b--94 95 72 72 513 72 31
-______
or hihgWi6 ---------or niorep ymerizable ursetureted groups per 4 4 4 4 4 4 4 Content of core-forming monomers [mass %J based on the total amount f traobunturd monomor having one % 96 s 06 96 N) core-torn g minorre component pol ia zabe unsat.vated group per r oleculs --- -Polynseriebio unieturetS pSeoner haQ!ng 01 - 83 35 or 02 alkyl group ______ ______ ______ ______
------
---Hydrophobia ooymerzab6 unsaturated monomer 13 22 51 52 61 (b-i) ---flpbLurfl TT7T Content o shell forming monomers [mass % based on the total amount rnonomar e-2 --I -rctwg manorer somponents Cathoxrconan ig p0 menzebb ureaturatsd -9 9 menemer(a-3) ---- ----. ----Polyrianzable unsaturated monomer (o4i other -then the pofrmflebk3 unsaturated monomers (b-70 61 22 22 19 22 4 1) to (b-3) ____________ ______ ______ ______ ______
-
Sohds Oontrt [%] 10 10 30 40 30 30 30
-
________ AodVskse[jrK0H'g 13 13 U 13 26 43 13 __________ z,saetrt0H'1 ___ ___ 17 9 ___ /-4 1-lf4 AfrA1-7 3 DSrzdater 40 40 4040 4040 7 - $R-1020 _________________ 8 29 8 is 20 4 1 -thykn gycE Poms abo attatd rr*nomer kvng 2 2 2 2 or more p ymerirthe wrnthrated groupe ---per PioeoJ AjF rneUorysto 1 1
_ -
*StyreElo 3 3 uroturathd rn000mar k-P itutyaoryatø 0 10 10 14 10 2 21 -v ---*----------Mororn nuson fir on -ocntanrig coro 4oioi,r Cornponeit Poymozahs pynorSbe 2-1iydroxyathy 12 2 monr,ri*r urs8turted morne' metheovote ore (b-2)
S _____________ ----------
C8rby---ocntthnin --unsaturtgd group tr poIyreñzbFe -:MeL'iecry:ec S 8 2 -mu eu t, unset4xetsd m000mer I 17usv orte 52 F unsotordted r;touomer --herg 01 or 02 thyhcrysts 2 o 2 9 13 3 11
-- -
0eorizedwetr -ii. I? 17 1 1? 1/ Adekeria Scep SR 1020 ___________________ 12 12 12 12 2Z - ?moior rn persuWats 003 003 C3 003 004 0P3 -
-
F1,drophot p ymsrnble sn.ureted E2__ 4jj3 mororrie (k-i 1 bLty auryleto 1 4 1 4 11 ---1--------_-Mo-ne oi,kon for Firoxy coraflng pos-r9e 4bIe yr aturte 2-hvdrozy4tn.A 9 2 2 mu rier (k-2:rnethstry:ete -__________ -+ --io-or r Cornponoc t Oath oori&siwig pc1yrnerrtabIa ur,satrated Methac 0 aod 2 0 0 9 9 2 2 moncrngr b3) ________________________________________ ----
--
froFymense Methsl methrrykte 0 5 3 4 Poynanrabla ksrtstjreted rroncrre _______________:8:e Ci or 02 s kgl Eth r4 r ---------___ ---____________________________ =W += 7=t C4S-A Aea -S. JL S.
-
Pm oton txarnçe ______________________________________ 4: f wwrJ 4We y,, 41-14 Al-lb Afr Ifs Al P A Ifs A119 Al 20
__________ __________ __________ --
Iota amoirt poiyrrensbIe tjnsetjrred mar mere 4n3VAntQ monomer $ 100 JO IJU JO 0O;O0 00 Iota amount o cc 4orrmng nonornew compor1rth etts, _______________________ 77 11 c2L4_.!.t 00
_______--
Toter amount or she rforrn;ng monomer -3 3: 2 23 4 0
S
Hydrophobo clrnerrzsbIe unsatu atari monomer 24 24 24 24 44 roxy-ntad pymsreb;tnsetureted 21 Content of each monomer [mass %] isseri on the toW emount of Imonomei (b-2) --pycnerebre unsaturated nonomers (amount of monomer component Cerbox-oananng pclymerebks unsaturatad 2 14 2 2 2 bonomerffr3) .. . Poymerizebk unsaturated monomer (b-4) other I [then the p ymarzabIrs uctureted orners (b-74 V9 74 58 72 72 72 h)to(b-3) ______ ______ ______ ______ &ymenzeWe unsaturated monomer hav:g two ror more poymcrzab!e unsaturated groups par 4 4 4 > 4 0 3 3 Content of corrtorrpng monomers [mass % based on the tot& amount;iyme;unturated monomer having R 97 of core-formeig monomer oomponrts payrnaraLra u saturateri group per moecre ______ ______ ______ ______ 83 6fs83f 68 87 72 69 nrC2&ky:group ____ ____ ____ ____ ____ ____ ____ oojnierizabk unsaturated 22 I 22 61 0
I
EHydraxy--oentarrrng poymerzabe unsaturated 2 monornsr(b--2) -Content of sheD rorEmng monomers [mass %3 based on the tota amount.
of end -forn Fk msnoner oorrpopenL Csrboxy-rora p ng poymer z?e unea 26: 2 2 9 50 monomer (b-3) [Poymerrzebe unsaturated monomer (b-4) other than the potyrrraseblo unsaturated monomers (b 28 13 28 13 22 0 1)to(b-3) _____ _____ _____ _____ _____ _____ _____ Sort1 Contsrr [%] 0 30 3u 3u 30 30 30 -...--- ___ Aod Vjm9ji. L. JL LL L 9 HywayV4ueKOH4 ____________ 2 91: jJ 39 9 9 4 l29- }Ynrther in Table 1O among the water-dispersible acrylic resin water dispersions (Ai-7) to (Ai-20) * (A1-7) to (Al- 17) and (Al-lY) correspohd to the core-she11-type water-dispersible:nyaroxv-containing acrylic resin (Ai'-l) * and (Al I) to At-i7) correspond to the coreshell-type water-dispersible hydroxy-containinq acrylic resin (Al' -2) ion Examples 229 to 275 and Comparative Examples 44 to 50 Aqueous coatino comnositions (XB5) to (X-133) havino a pH of 8.0 and a sonds content of 2o% were ohuained ifl tixe re maimer as in Examole I, except that the formulation co position shown in Tab].e 11 was used
[Table 11] Thblc
FutrnpIe i30 231 232 n423s?neJ siT 2.13
LI
I Mt'r dsp* IvP *3-i M-A1-41-'? 41-? Al-'? A-'? 41-81 4?-'? 4.1-s w r,f w#ic-1 1knin (At' 4 f*r4c 3urtt, 1QU Wi) 100 t00 101) 301) 11)0 103) 300 300 rs r -3) 51) 50 51) Q 50 50 51) 53 3 53) ] t:Te AZ-i #25 3 #JEItAM ---.
p4t4st.ta ?aaø4y 41 43 43 43 43 43 43 43 43 43 . A>33,nr 1$ 38 133 t 1-31 18 133 58 133 H 113 tP-lPj4yH 1LL PH P-I LIthJ 5so,q y a 1ar of Is[Pr co-i co cci oca oo ao oos 01)6 Vcositv V, k e rate cl bar of ft1rt'[Pr 3'? 4'? itt _______ ______________________________________________ ______
--
--23. 11)4 -4 & S J-s zos o; os1 xs -soo xioi c rt4'd 5 l,r-, oc IY 10 S lr IC OC IflSI 4 L-*l Rt.114 6151 64F2i-6 RO *0 V)1_Q_ I rJrres i6sa 5 1&sr d6ptr?SL. ii M-9 *1-4 *1-4 Al-S Al-j Al -4 Al-i 41 41-) Al-16 61S. tstn A1 dolylk I4y 1053 01 1613 105 00 530 0 1053 01 01 lO5 CC SO'S 100 6531110 I rn ___! Atrytnssn t4t:tJ iii j3 t± -ipic. p-I p-l1p-.s-p--!p--1 p-i -ip-s p.-p--i p--s czv r r'ir r ir rIrirr + -*---AstyVflr,reMss2,ro0IC,1r *06 006 0534 0A36 004 5304 O5 9145 094 645 046 046 041 004 flP-teoJ - ;ia,-rpr 77I TTT T"771T 4:4t j1-.-,t: ---- --________ -26 AtT:,po,aor --xTo*fi-nä x-ni -li±-Wd' dssçssrsaon j... *51 414 41-9 41-01 *5-9 *5-0 M-1 45-0 r53-°1 3) 304) 35W -IOU 1130 105 500 100 ii±___ i:iE r 00 M6rr15907 ZA*4) _____ -------I 42 I, Slsr---om 09 6 1*SI' 18 TI:;c3ç?:s VostV1atort*af*harnt11)3K$so Po-soc] 4 £000 (107 OUs £00.5 a oi.0.. -0e 5105 5105 -t --g::y:t*cste Mshevth01ai'a-n JJ$jj$L ±ILLLL Tbi 1 3-4 353 54 263 296 287 209 1230 27(1: -- - tEc, X-323,4*-lfl( 20 %!?? TtWf!f L!E J L1.±JL LdJ__-______ csr(A1., 3(10 1% 120 300 ICC 00 300 30(1 Wi 300
-
:50 5014050 20 30t505D50 50.
- H I
421 421&&1 %2-42-S 42-lf\2-42-k?-! Al-I PQ *" ---------c3Ei r9sn 19 38 1 :;;;, i:::::: :E::t:r:a: j*i: ::Ia: :a ---a JL S S S S S S S S Lt,c.fthiw of o[Po-zeo] OSlO 008 003 0438 (405 3107 0434 006 <8(19 005 42 83 (34 57 27 t9(l31 11-5 ________________ _______________ ___________ ______ Cornoe,.tiyc E,ceoIe 274275 444(3 46.4? 44.40 30 --------% -Aqt.o.sz 0*atng G4rpos-bcn 3<123 X130 Y 33 3< 32 K-Ifl)r 34 X 13 X 334 5 3' 5 138 &C?33 30 tr4(9o f439 3(1 SM Ic' 3(14 130 lOS l(# 0-t4r1uidcfcom4vnz, * (192n1I1 S 6 6 * * *3 & *3 4, .., W3k6 jcon,( 1c'& A3-29 43-9 41-9 43-9 4 -9 53 9 51 9 414 41-9 4-0 i': --%-----%------------------------------------------i÷ii agsfl fl) e3s,ic-vo 3.13 93 353 31 30 30 13 0 5* (30
-
t06 2 I N' 2 423 52 *3 3 4? 3 A?3 52-I 42-i --ro6r_ s42sn. -S V -4It$3< 43 P3.43 43 43 43 4.43 43 3 (3 9 43 49 35 I IL 1? U 38 13 T1-06 L1 -i P-1P-l P-33.p--3.31_5 P-l a c4xI-g9 939,lflct d,,?sor3 ----------"---!JL LLSm ?sc t03l T"° 13Y 821 <a; 49 r ?locc0t,VtrM.oE4.r of08fl,i:'(pr,rnc0. <8' 003 (1332. 004 3102 (400 3104 ___________________..tLtiiTL 111 (Note 4) Melamine resin (B-2) same as desrri.hed above.
(Note 5) 53Bayhydur VPLS2E1U": same as described above.
(Note 6 ACRYSOL RM-825": same as described ajo Method of Fanning Ccat.tnq Films Examples 276 to 322 and Comparative Examples 51 to 57 Test panels of Examples 276 to 322 and Comparative ?xanipies 51 to 57 were obtained in the same. manner as in Example 56, except that the aqueocs coating composition shown in Table 12 was used in place of the aqueous coating composition (K--I) Eva1ua on Test 3 Each test panel-obtained in Examples 276:o 322 and Comparative Examples 51 to 57 was tested for smoothness, 001, flip-flop property1 metallic mottling, and water resistance. The test methods are as fo].lows: Smoothness: Smoothness was evaluated for each test paneJ.. based on the Long Wave (LW) values measured by Wave Scan" (product name, manufactured by BYK-Gardner) The lower the LW value, the higher the smoothness of the coated surface.
001, flip--flop property, metallic mottling, and water resistance were tested arid evaluated according to the method described in the Evaluation Test 1.
For coating vehicles and the like in the I i.eld to which the present invention pertains, high smoothness is pref:erred, in addition to excellent tOt, f lip-flop property, metallic mott I Ing, and water res-rstance. A.ccordi.ngry, in the Evaluation Test 3, the comprehensive evaluation was conducted according to the following criteria: A: The smoothness ((LW) value) is 10 or lower, 001 C SW) value is 12 or lower, and all of the flip--flop oroperty, metallic mottling, and water resistance are A. B: The smoothness ( LW) value) is 10 or iower 001 ((SW) value) is 12 or lower, and each of the f.l.ip--flop property, metallic mottling., and water resistance is either A or B, with at least oneoftheinbeingB.
C: The smoothness ((LW) value) is 10 or lower, 001 ((SW) value) is 12 or lower, and each of the flip-flop property, metallic mottling, and water resistance is A, B, or C, with at. least one of them being C. 0: The smoothness ((LW) value) is Il or higher, DO-i ((SW) value) is 13 or higher, or at least one of the flip-flop property.
metallic mottling, and water resistance Is 0.
Table 12 shows the test results of the coating film performance.
[Table 12]
Tabe 12--______ Aqueous F -Water Ccmprehensiv Srnothness Rip-&p Matic res:tao svarnt:on property mttn X96 SA A B !! ±!L. LLL A4 289 X--98 9 9 [3 A [3 B 2 X-99 7 8 A A A A
-
28t *101 7 8 A B A B
--------------
294 X-103 7 9 B B A B ___ iIi.TJ1.
296 *105 9 8 S A A B 29 X-106 7 9 [3 A A B 309 X-lIZ 10 10 [3 A B B 2flEcr 303 *114 6 t 8 A A A A A-1 a ______ AD A B X7 A-116 9 7 [3 B A B o8 X-117 2) 6 [3 831 83 r mrr flflJLL : 34-Las r -w&er compr,ensi,e mpouidon Srnthnes flp-flap MeteBt rtstnt-s vautefl property F'ott.w ni:::: 3 X--14.. 8 U B B B Ebarnps 12 H 7,. A La A 8 10 A B B QJL.. B B 1t *-ua B B A B B S x--n a B B 22 X-fli B 8 B I B A B 32 54fl A 0 I52 XH33 27 27 0 A 0 > .c:L:cLi: ______ Cornparetdv Exarnpl) 15 25 -18 0 0 A 0 56 6. 10 j C C. A 0 L!Q Jt9'. I
A U

Claims (13)

  1. Ciaims [Clairni] Acopolymerobtainablebycopolymerizationof amonomer component mixture(m) comprising: (rn-i) a macromonomer having (i) a backbone that comprises a polymer chain having a number average molecular weight of 1,000 to 10,000 obtainable by polymerizing a monomer component (I) that contains 5 to 100 massi of a 04-024 alkyl-containing polymerizable unsaturated monomer (a) , and (ii) a polyrnerizable unsaturated group; and (rn-2) a polymerizable unsaturated rnonomer containing a hydrophilic group.wherein the copolymer is a graft polymer having a rnain chain and a side chain, component (m-2) is a polymerizable unsaturated monomer containing at least one kind of hydrophilic group selected from the group consisting of acrylic acid and methacrylic acid, and wherein the content of component (m-1) is in a range of from 1 to 40 massi, and the content of component (m-2) is in a range of from 5 to 75 massi, based on the total mass of monomer component (m) , or component (m-2) is a nonionic polymerizable unsaturated monomer containing at least one kind of hydrophilic group selected from the group consisting of N-substituted (meth)acrylamide, polymerizable unsaturated monomer having a polyoxyalkylene chain, and N-vinyl-2-pyrrolidone, and wherein the content of component (m-1) is ma range of from 1 to29mass%, and the content of component (m-2) is in a range of from 20 to 99 mass%, based on the total mass of monomer component (m) provided that a graft copolymer consisting of: (A) a main chain containing an N-substituted (meth)acrylamide compound in a monomer component and having a lower critical solution temperature in water of 40°C or higher; and (B) a hydrophobic side chain is excluded.[Claim 2] The copolymer according to claim 1, wherein component (m-2) is anonionicpolymerizable unsaturated monomer containing at least one kind of hydrophilic group selected from the group consisting of N-substituted (meth)acrylamide, polymerizable unsaturated monomer having a polyoxyalkylene chain, and N-vinyl-2-pyrrolidone, and wherein the content ot component (m-1) is in a range of from 1 to 29 massf, and the content of component (m-2) is in a range of from 20 to 99 mass%, based on the total mass of monomer component (m) [Claim 3] The copolymer according to claim 2 wherein monomer component (I) contains, at least a part thereof, 5 to 60 mass% of a hydroxy-containing polymerizable unsaturated monomer, based on the total mass of monomer component (I) [Claim 4] The copolymer according to claim [1], wherein component (m-2) is a polymerizable unsaturated monomer containing at least one kind of hydrophilic group selected from the group consisting of aorylic aoid and methacrylio acid, and wherein the content of component (rn-i) is in a range of from 1 to 40 massi, and the content of component (m-2) is in a range of from 5 to 75 mass%, based on the total mass of monomer component (m) [Claim 5] The copolymer according to any one of claims 1 to 4 or 2,wherein the monomer component (I) comprises a polymerizable unsaturated monomer having a C6-C18 alkyl group.[Claim[6]Ai aqueous coating composition containing the copolymer according to any one of claims 1 to 5and a film-forming resin (A) [Claim [7] The aqueous coating composition according to claim 6, wherein the film-forming resin (A) comprises a water-dispersible hydroxy-containing acrylic resin (Al') having an acid value of 1 to 100 mg KOH/g and a hydroxy value of 1 to 100 mg KOH/g, obtainable through copolymerization of monomer component Kb) comprising 5 to 70 mass% of a hydrophobic polymerizable unsaturated monomer (b-i), 0.1 to 25 mass% of a hydroxy-containingpolymerizable unsaturatedmonomer (b-2) , 0.1 to 20 mass% of a carboxy-containing polymerizable unsaturated monomer (b-3) , and 0 to 94.8 mass% of a polymerizable unsaturated monomer (h-4) other than the polymerizable unsaturated monomers (b-i) to (b-3) [Claim 8] The agueous coating composition according to claim 6 or 7, wherein component (m-2) comprises at least one kind of polymerizable unsaturated monomer selected from the group consisting of N-substituted (meth)acrylamide, polymerizable unsaturated monomer having a polyoxyalkylene chain, N-vinyl-2-pyrrolidone, 2-hydroxyethyl acrylate, acrylic acid and methacrylic acid.[Claim 9] The aqueous coating composition according to any one of claims 6 to 8, wherein monomer component mixture (m) contains 1 to 40 massi of component (m-l) and 5 to 99 massi of component (m-2) , based on the total mass of monomer component mixture (m) [Claim 10] The aqueous coating composition according to claim any one of claims 7 to 9, wherein the water-dispersible hydroxy-containing acrylic resin (Al') is a core-shell-type water-dispersible hydroxy-containing acrylic resin (A1'-i), which has a core-shell structure having, as a core, copolymer (I) containing, as monomer components, 0.1 to 30 massi of a polymerizable unsaturated monomer having two or more polymerizable unsaturated groups per molecule and 70 to 99.9 massi of a polymerizable unsaturated monomer having one polymerizable unsaturated group per molecule, based on the total mass of monomer components constituting the core, and wherein the core-shell-type water-dispersible hydroxy-containing acrylic resin (Al'-i) contains 5 to 70 mass% of a hydrophobic polymerizable unsaturated monomer (b-i), 0.1 to 25 massi of a hydroxy-containingpolymerizable unsaturatedmonomer (b-2) , 0.1 to 20 massi of carboxy-containing polymerizable unsaturated monomer (b-3) , and 0 to 94.8 mass% of a polymerizable unsaturated monomer (b-4) other than the polymerizable unsaturated monomers (b-i) to (b-3), based on the total mass of monomer components constituting the core and the shell.[Claim lii The aqueous coating composition according to any one of claims 7 to iO, wherein the water-dispersible hydroxy-containing acrylic resin (Ai') is a core-shell-type water-dispersible hydroxy-containing acrylic resin (A1'-2) comprising a core portion that is a copolymer (I) consisting of, as monomer components, 0.1 to 30 massi of a polymerizable unsaturated monomer having two or more polymerizable unsaturated groups per molecule and about 70 to 99.9 massi of a polymerizable unsaturated monomer having one polymerizable unsaturated group per molecule; and a shell portion that is a copolymer (il) consisting of, as monomer components, 5 to 80 rassl of a hydrophobic polymerizable unsaturated monomer (b-i), 0.1 to 50 mass% of a hydroxy-containing polymerizable unsaturated monomer (b-2), 0.1 to 50 massi of a carboxy-containing polymerizable unsaturated monomer (b-3) , and 0 to 94.8 mass% of polymerizable unsaturated monomer (h-4) other than the polymerizable unsaturated monomers (b-l) to (b-3), and wherein the solids content mass ratio of oopolymer (I) to oopolymer (II) is in a range of 5/95 to 95/5.[Claim i2]The aqueous coating composition according to any one of claims 6 to ii, wherein the film-forming resin (A) comprises a resin having an ester bond.[Claim 13] The aqueous coating composition according to any one of Claim 6 to i2, wherein the film-forming resin (A) comprises a water-dispersible acrylic resin obtainable by emulsion polymerization using a surfactant.[Claim 14] Aarticle coatedwith the aqueous coating composition according to any one of claims 6 to i3.[Claim 15] A method for forming a multilayer coating film, comprising the steps of: (1) applying the aqueous coating composition of any one of claims 6 to 13 to a substrate to form a base coating film; (2) applying a clear coating composition on anuncured base coating film to form a clear coating film; and (3) heating the uncured base coating film and uncured clear coating film to simultaneously cure both coating films.[Claim l6]A method for forming a multilayer coating film, comprising the steps of: (1) applying a first coloring coating composition to a substrate to form a first colored coating film; (2) applying the aqueous coating composition of any one of claims 6 to 13 on the uncured first colored coating film to form a second colored coating film; (3) applying a clear coating composition on the uncured second colored coating film to form a clear coating film; and (4) simultaneously heat-curing the uncured first colored coating film, uncured second colored coating film, and uncured clear coating film.[Claim 171 An article having a multilayer coating film formed by the method according to claim 15 or 16.[Claim 18] A viscosity-controlling agent comprising the copolymer according to any one of claims 1 to 5.[Claim 19] Use of the copolymer according to any one of claims 1 to 5 in the control of viscosity of an aqueous coating composition.[Claim 20] Use of the copolymer according to any one of claims 1 to 5 in the manufacture of viscosity-controlling agent.AMENDMENTS TO THE CLAIMS HAVE BEEN FILED AS FOLLOWS: Claims 1. A copolymer obtainable by copolymerization of a monomer component mixture(m) comprising: (rn-i) a macromonomer having (i) a backbone that comprises a polymer chain having a number average molecular weight of i, 000 to iO, 000 obtainable bypolymerizing a monomer component (I) that contains 5 to i00 rnass% of a C4-C24 alkyl-containing polymerizable unsaturated monomer (a), and (ii) a polyrnerizable unsaturated group; and (rn-2) a polyrnerizable unsaturated monomer containing a hydrophilic group, wherein the copolymer is a graft polymer having a main chain and a side chain, component (m-2) is a polymerizable unsaturated monomer containing at least one kind of hydrophilic group 0 selected frorn the group consisting of acrylic acid and methacrylic acid, and wherein the content of component (m-l) is in a range of from 1 to 40 massi, and the content of component (m-2) is in a range of from 5 tc 75 massi, based on the total mass of monomer component (m) , or component (m-2) is a nonionic polymerizable unsaturated monomer containing at least one kind of hydrophilic group selected from the group consisting of N-substituted (meth)acrylamide, polymerizable unsaturated monomer having a polyoxyalkylene chain, and N-vinyl-2-pyrrolidone, and wherein the content of component (m-l) is in a range of from i to 29 massi, and the content of component (m-2) is in a range of from 20 to 99 mass%, based on the total mass of monomer component (rn) provided that a graft copolymer consisting of: (A) a main chain containing an N-substitllted (meth) acrylamide compound in a monomer component and having a lower critical solution temperature in water of 4000 or higher; and (B) a hydrophobic side chain is excluded.
  2. 2. The copolymer according to claim 1, wherein component (m-2) is a nonionic polymerizable unsaturated monomer containing at least one kind of hydrophilic group selected from the group consisting of N-substituted (meth) acrylamide, polymerizable unsaturated monomer having a polyoxyalkylene chain, and N-vinyl-2-pyrrolidone, and wherein the content of component (m-1) is in a range of from 1 to 29 massi, and the content of component (m-2) is in a range of from 20 o 99 massi, based on the total mass of monomer component (m)
  3. 3. The copolymer according to claim 2 wherein monomer component (I) contains, at least a part thereof, 5 to 60 mass% 0 of a hydroxy-containing polymerizable unsaturated monomer, based on the total mass of monomer component (I) r
  4. 4. The copolymer according to claim [1], wherein component (m-2) is a polymerizable unsaturated monomer containing at least one kind of hydrophilic group selected from the group consisting of acrylic acid and methacrylic acid, and wherein the content of component (m-1) is in a range of from 1 to 40 mass%, and the content of component (m-2) is in a range of from 5 to 75 massl, based on the total mass of monomer component (m)
  5. 5. The copolymer according to any one of claims 1 to 4 or 2,wherein the monomer component (T) comprises a polymerizable unsaturated monomer having a 06-018 alkyl group.
  6. 6. An aqueous coating composition containing the copolymer according to any one of claims 1 to 5_and a film-forming resin (A).
  7. 7. The aqueous coating composition according no claim 6, wherein the film-forming resin (A) comprises a water-dispersible hydroxy-containing acrylic resin (Al' having an acid value of 1 to 100 mg KOH/g and a hydroxy value of 1 to 100 mg KOH/g, obtainable through copolymerization of monomer component (b) comprising 5 to 7Omass% of a hydrophobic polymerizable unsaturated monomer (b-i), 0.1 to 25 mass% of a hydroxy-containing polymerizable unsaturated monomer (b-2) 0.1 to 20 mass% of a carboxy-containing polymerizable ct unsaturated monomer (b-3), and 0 to 94.8 mass% of a polymerizable llnsaturated monomer (b-4) other than the polymerizable unsaturated monomers (b-i) to (b-3)
  8. 8. The aqueous coating composition according to claim 6 or 7, wherein component (m-2) comprises at least one kind of polymerizable unsaturated monomer selected fron the group consisting of N-substituted (meth) acrylamide, polymerizable unsaturated monomer having a polyoxyalkylene chain, N-vinyl-2-pyrrolidone, 2-hydroxyethyl acrylate, acrylic acid and methacrylic acid.
  9. 9. The aqueous coating composition according to any one of claims 6 to 8, wherein monomer component mixture (m) contains 1 to 40 massf of component (m-l) and 5 to 99 mass% of component (m-2), based on the total mass of monomer component mixture (m).
  10. 10. The aqueous coating composition according to claim any one of claims 7 to 9, wherein the water-dispersible hydroxy-containing acrylic resin (Al') is a core-shell-type water-dispersible hydroxy-containing acrylic resin (A1'-l), which has a core-shell structure having, as a core, copolymer (T) containing, as monomer components, 0.1 to 30 mass% of a polymerizable unsaturated monomer having two or more polymerizable unsaturated groups per molecule and 70 to 99.9 mass% of a polymerizable unsaturated monomer having one polymerizable unsaturated group per molecule, based on the total mass of monomer components constituting the core, and wherein the core -shell -type water -dispersible hydroxy-containing acrylic resin (Al'-l) contains 5 to 70 massi of a hydrophobic polymerizable unsaturated monomer (b-i), 0.1 to 25 massl of a hydroxy-containing polymerizable [5 unsaturated monomer (b-2), 0.1 to 20 massf of (0 carboxy-containing polymerizable unsaturated monomer (b-3) 0 and 0 to 94.8 massf of a polymerizable unsaturated monomer (b-4) other than the polymerizable unsaturated monomers (b-i) to (b-3), based on the total mass of monomer components constituting the core and the shell.
  11. ii. The aqueous coating composition according to any one of claims 7 to 10, wherein the water-dispersible hydroxy-containing acrylic resin (Al') is a core-shell-type water-dispersible hydroxy-containing acrylic resin (Al'-2) comprising a core portion that is a copolymer (I) consisting of, as monomer components, 0.1 to 30 masst of a polymerizable unsaturated monomer having two or more polymerizable unsaturated groups per molecule and 70 to 99.9 massi of a polymerizable unsaturated monomer having one polymerizable unsaturated group per molecule; and a shell portion that is a copolymer (II) consisting of, as monomer components, 5 to mass% of a hydrophobic polymerizable unsaturated monomer (b-i), 0.1 to 50 massi of a hydroxy-containing polymerizable unsaturated monomer (b-2), 0.1 to 50 mass% of a oarboxy-oontaining polymerizable unsaturated monomer (b-3) and 0 to 94.8 massi of polymerizable unsaturated mcnomer (b-4) other than the polymerizable unsaturated monomers (b-i) to (b-3) , and wherein the solids content mass ratio of copolymer (I) to copolymer (II) is in a range of 5/95 to 95/5.
  12. 12. The aqueous coating composition according to any one of claims 6 to II, wherein the film-forming resin (A) comprises a resin having an ester bond.
  13. 13. The aqueous coating composition according to any one of [5 claim 6 to 12, wherein the film-forming resin (A) comprises (0 a water-dispersible acrylic resin obtainable by emulsion 0 polymerization using a surfactant. Co14. An article coated with the aqueous coating composition according to any one of claims 6 to 13.15. A method for forming a multilayer coatinq film, comprising the steps of: (1) applying the aqueous coating composition of any one of claims 6 to 13 to a substrate to form a base coating film; (2) applying a clear coatinq composition on an uncured base coatinq film to form a clear coatinq film; and (3) heating the unoured base coating film and uncured clear coating film to simultaneously cure both coating films.16. A method for forming a multilayer coating film, comprising the steps of: (1) applying a first coloring coating composition to a substrate to form a first colored coating film; (2) applying the aqueous coating composition of any one of claims 6 to 13 on the uncured first colored coating film to form a second colored coating film; (3) applying a clear coating composition on the uncured second colored coating film to form a clear coating film; and (4) simultaneously heat-curing the uncured first colored coating film, uncured second colored coating film, and uncured clear coating film.17. An article having a multilayer coating film formed by the method according to claim 15 or 16.18. A viscosity-controlling agent comprising the copolymer according to any one of claims 1 to 5.19. Use of the copolymer according to any one of claims 1 to 5 in the control of viscosity of an agueous coating composition.20. Use of the copolymer according to any one of claims 1 to 5 in the manufacture of viscosity-controlling agent.
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