Title of Invention


Abstract The present invention relates to a coating finishing method comprising coating a comprising coating material (I) on a surface of a metal substrate or an old coated face of a metal substrate and then coating a water based coating material (II) comprising a water based fatty acid modified acryl resin as a base resin component, wherein the above water based coating material (11) contains a pigment in a pigment volume concentration falling in a range of 5 to 45 %, and the above water based fatty acid-modified acryl resin has a form of a fine particle having an average particle diameter falling in a range of 50 to 500 nm. According to the method of the present invention, capable of being for4eld is; a finished coating film which has a good finished appearance and which can maintain a fine view of metal surfaces used for structures such as buildings, bridges and plant facilities over a long period of time.
Full Text

'Ifedbnica I l The present invention relates to a coating finishing method for a metal substrate surface or an old coated face on a metal substrate usin? a water-based coating material which is suited fox maintaining a fine view i;;»f structures such as buildings, bridges and }3]ant facilities uv&r a long period of time.
Backgroiiiici. Art
In general, solvent base top coating: materials such as an alkyii resin base coating material, an acryl alkj^d resin base coating material a i-iilicon aJlcyd resin base coating material and a phthalic
acid resi):. b:;;ise enamel coadng material are coated on the surfaces of striictiires sach as buildings, bridges, plant facilities and steel towers after coatiniif; rust preventive coating materials. Such coating step compriseH usually coating once or twice a rus t preventive coating material and then coating thereon once or twice a top coacing material ■■mch as a phthalic acid resin base enamel coating material,
and the cc'ating step as desired to be shortened from an economical point of viBw, Further, in recent years, erivir'onmental protective counternieasures such as a rise in working; environment and a stre:c gtheik in environmental regulation hfive become social subjects, and therefore a non-environmental pollution type water-based
coating sj/stum has come to be required more and more strongly.
It 1,3 Imown as a water based coatiiig system which is coated on a metiil liiace to coat a water-based rust preventive coating material cjociiprising a water-based alkyd resin as a base resin component and then coat thereon a top coating material comprising an acryl resin emulsion as a base resin component.
Hcnvever, the existing situation is that the top coating material comprising an acrjd resin emulsion as a base resin component, forms a film by fusion of acryl resin emulsion particles
and thereibite has a low finishing property'(glossiness) after coating ind that it m not reliable as compared with a solvent base coating

systeim iij the point that the coating tilm tbrmed has an ansatisfi3.::tcry gas-barrier property of oxygen and steam. Thus, required i:o he developed is a water-based coating system in which the same perlitrmance as in coating by a solvent type coating material is exhil)il:ed by coating a waterbased coating material on the surface of metals.
0;ii the other hand, coating material compositionie comprising a water-l'iEi s(i:'d fatty acid-modified acryl resin having both of the iunctions of a water-based alkyd resin and a water-based acryl resin are disclosed in Japanese Patent Apphcation Laid-Open No. 8773/1984 and Japanese Patent Application Laid-Open No. 319525/2000. It is described in the above publications that the above coatirig material compositions form coating films having an excellent ccirosion resistance and is suited as a primer for a metal face,, Hovi^i^ver, there is in^7c»lved therein the problem that the coating fiJ.mi!:; formed are unsatisfactory in a water resistance and a weatherabiilLity attributable to the fatty acid component which is a soft com|:ni;i'n:mt, and. mere coating of the above coating material compositii'Dniiii oa the surface of a metal substrate can not sufficiently proteci;; the surface of the metal over a long period of time.
Discloiiiiu^?! o,f the In'i^intioii
A prijicipal object of the present invention is to provide a coatiag fuiishing method by a water-basedj coating material which shovi^s a gQod finished appearance and which can maintain a fine view of mi?tsil surfaces used for structures such as buildings, bridges and plant iai:;ilities over a long period of ti^^e.
The present inventors have found that the object described above can m achieved by a coating finishihg method in which a wate:r-based under coating material is coated on a metal substrate md in which, a waterbased coating material comprising a water-ijasecl fatty acid-modified acryl resin having a specific average particle diameter as a base resin component and containing a pigment in a specific concentration is coated on the coated face thereof, a]id they have come to complete the present invention.

Tlius;., the present invention provides a coating finishing method cotnprising coating a water-based;under coating material (I) on a siirtace of a metal substrate or an old coated face of a metal
substrata? and then coating on a coated surface thereof, a water based coating material (II) comprising a water-based fatty acid-modified acryl resin as a base resin component, wherein the above water-based (ioating E:.iaterial (II) contains a pigment im a pigment volume concetitriyiicm falling in a range of 5 to 45 %, and the above water based fatvy acid-modiified aciyl resin has a form of a fine particle havrig a;n average particle diameter falhrlg in a range of 50 to 500 nm.
Tilt::' li'/ater-based coating material (IT) used for the method of the present mvention is excellent in a film-forming property and a glossiness aad can provide the formed coating film with a gas-barrier property by the fatty acid component which is a soft component and cross"liakiii!:!:, and therefore it can inhibit gases such as steam and oxygen from reaching an under coating film.. Further, bleeding of rust and a blistering phenomenon can be xeduced by providing a coating film by the water-based under coating material (1), and therefore according to the present invention, a finished coating film which prote<:ts a metal face over long period of time can be formed.> The iQethod of the present invention shaU be explained below in furtheir details.
Tht' substrate surface to which the method of the present invention can be applied includes the surfaces of metals such as iron, aluminurti and the lili:e and old faces on wiich coated are coating tiaateriaLs of an alkyd resin base, an acryl alkyd resin base, a silicon ilkyci resin Imse, an acryl resin base, an acryl urethane resin base, a polyureth.ane resin base, a fluororesin base, a silicon acrjd resin base, I vin>d acetate resin base and an epoxy resin base (hereinafter they ishall be cEiQed "metal substrate surface" as a general term). The nethod of the present invention is particularly suited to finish i;oating oi' a steel substrate or an old coated face on the surface of a iiteel subs Drate.
In Jie method of the present invention, the water-based under

coating material (I) is coated for the purpose of inhibiting corrosion on the sur&ice of a metal substrate and,bleeding of rust and controlling ivnevenness on a surface to fee coated by providing a film between r.he surface of the metal substrate and a coating film formed by tb.e wa.te'c-based coating material (II) described later. A water-based under coating material and a base controlling agent which are convention;nlly known can be used as the water-based under coating material (I).
Vari<: waterbased resins which are conventionally known as those us for coating materials can be used the base resin componert in water-based under material described above and capable of being given example acryl uretliane epoxy aliiyd fatty acid-modified resms resins. method present invention at least one selected ft group coruiiiisting alkyd is preferably from that they have a good compatibility v metal face ure excellem well an adhesive property to film i by later.> The virater-based under coating material (I) described above
preferably contains a pigment in a higher pigment volume
concentrjiticn than that of the waterbased coating material (II) for
the purposes of inhibiting bhstering in the finally obtained multilayer
coating filju from being generated and cbnstroJling unevenness on a
surface to be coated, and it preferably contains a pigment in a
pigment volume concentration falling in airange of usuaHy 30 to 50 %,
particulai'ly 34 to 4(5 %. j i
In th;i.s respect, the "pigment volikme concentration' is a
I !
volurae proportion of the above pigment based on the total sohd matt3r of the whole resin cotoponents and|the whole pigments i^ontsinecl in the coating material. In the;present specification, a specific giavity of the pigment which is ja ground for calculating a volurae of the pigment is referred to PaikitjRaw Material Manual sixth edlt].on edited by Japan Paint Industry i^sociation, and it is

assumed t:h;at a specific gravity of the resin is approximate to 1,
TlfiO ]:»igment which is blended with the water-based under coatini? ni^icerial (I) includes, for example J color pigments such as titanium white and red iron oxide; extender pigments such as calcium carbonate, magnesium silicate hydrate, talc, mica, clay and barj^ta; a:iid rust preventive pigments such as phosphoric acid base pigments and a phosphoric acid base pigment is preferably blended as a part of the pigment ixom the viewpoint of the corrosion resii3tance. Capable of being given as thd phosphoric acid base pigment are, for example, 2;inc phosphate, phospho •zinc:^silicate, alurninuni zinc phosphate, calcium zinc phosphate, calcium phosphate?!. Mluminum pyrophosphate, calcium pyrophosphate, aluminum tripolydihydrogenphosphate, aluminum metaphosphate, calcium metaphosphate, zinc phosphomolybdate and aluminum phosphoriiolybdate. They can be used alpne or in combination of two or more kinds thereol:. A blending amount of the above phosphoric acid oase pij^ment falls suitably in a range of 0.1 to 25 %, preferably 1 to 20 % in terms of a pigment volume concentration.
The water-based under coating material (I) described above :an conti3.:Li!i, if necessary, at least one of copventional additives for a coating mati^rial such as hydrazine derivatives described later, metal ciryeJ'S. Hash rust inhibitors, aldehyde scavengers, pigment dispenisantis, surface controlling agents, U\^ absorbers, defoaming ;igen[;s, tliickeners, curing catalysts, precipitation preventives, film-forming aid=i, antifreezing agents and antiseptic agents.
The -vir^ater^based under coating matierial (I) described above ::an be coi-i>ted in a coating amount falling i^ a range of usually 0.05 to }.5 ki^/m^, pi-eferably 0.08 to 0.3 kg/m^, and it can be coated by means )f a coatiing instrument such as a roller, ari air spray, an aiirless spray, I lithin gijin, a universal gun and a brush.; The coating film L-hickuess can fall in a range of usually 15 to 150 pm, preferably 24 to 90 pm in terms of a dry film thickness.
Ths drying conditions of the water-based under coating
naterial (1) described above shall not specifically be restricted and
-van be chismged according to the kind of the water-based under

coating nial/arial, and it can be dried;as well at a temperature of about 40"0 i:ir less. The drying tim(^ at ahmt 25°C can be, for example, 1 to 720 hours, preferably 2 to 336 hours after coating.
Tine ^vater-based coating material (ID coated on a surface on which thii! water'bai5ed under coating material (I) described above Ls coated actiording to the method of th6 present invention contains as a base resi:ri component, a water-based fatty acid-modified acryl resin having a ]:o:irm of a fine particle having an average particle diameter fallirLg in a range of 50 to 500 nm, pairticulariy 75 to 400 nm and further pardcuilariy 100 to 250 ma. If the waterbased tatty acid-modified J3,c:ryl resin has an average particle diameter of less than 50 nm, not only the coating material is increased in a viscosity to make it difficult; to form a smooth coating film, l^ut also the state of the coating nuitiitrial after storage at a low temperature is reduced. On the other hand, if the average particle diameter exceeds 500 nm, a storage stability of the coating material becomes unsatisfactory and the film-foriiimg property is reduced. Farther, the coating film formed is re'iuced as well in a gavS-barrier property, and therefore the
libove 'IS 15(11; preferred. In the presept specification, the average parti?le d iameter is a value obtained|by measuring the sample
diluted ti> a concentration suited to the measurement with deionized wate:r at a room temperature (about 30'C):by means of "Si^D-3100" !trads nanui^ a laser diffraction type particle size distribution cieasuidiig apparatus, manufactured!by Shimadzu Mfg-.'Co., Ltd.).
Sviited as the water-based fatty acid modified acryl resin described above is, for example, a resin comprising a structural unit Jerived ft'Oin a fatty acid (a), an epoxy growp-containing polymerizable unsaturated monomer (b), an acid group-oontaining polymerizable unsaturated monomer (c), a| polymerizable ij,nsai:urated monomer (d) having an ^liyl 'group having 4 or more jarbon atoms and the other polymerizableiunsaturated monomer (e).
Ttis fatty acid (a) includes fattjy acids hairing a structure in
;^rhich a carhioxyl group is bonded to an en4 of a hydrocarbon chain, ;md dmn-g' oil fatty acids, semi-drying oil fatty acids and non-drying oil fai:ty acids can be given as the exajmple^ thereof. The drying oil

tatty acicis can not sincuy ne aistanguisnea irom ine senirarying on
i i
fatty acids. In general, the drying; oil fatty acids are unsaturated
tatty acids ttaving an iodine valuo of! 130 or more, and the semi-
drying oil fatty acids are unsaturated fatty acids having an iodine
value of 100 or more and leiss than 130. Further, in general, the
non-iliyinf? oH fatty acids are unsaturated fatty acids having an
iodiri.e vaiius of less than 100. The d^^yn^g oil fatty acids and the
semi-dryiiijij oil fatty acids include, for example, fish oil fatty acid,
dehydrated caf^tor oil fatty acid, saffiower oil fatty acid, linseed oil
fatty acid, s-oybean oil fatty acid, ses^ime oil ftitty acid, proppy seed oil
fatty acid, perila oil fatty acid, hemp-seed oil fatty acid, grape nucietis
cal fatty add;, corn oil fatty acid, tall Oil fatty acid, sunflower oil fatty
acid, cotton seed oil fatty acid, walnut oil fatty acid and sesame seed
oil fatty acid. The non-drj'ing oil fatty acida include, for example,
coconut cil :Eiiitty acid^j, hydrogenatedi coconut oil fotty acids and palm
oil fatty mids. They can be used alone or in combination of two or
more kinii'5 thereol Caproic acid, capric acid, lauric acid, myristic
ELcid, palmitic acid and stearic acid can be used in combination
therewith. I
In the present invention, the drying oil fatty acid and/or the
iemi'dry-.tig oil fatty acid are suitably used as the fatty acid (a) because cd' an excellent oxidation curing property and an excellent is;as-t arrier property of the coating fL^m formed.
The g^poxy group-containing pplymerizable unsa&irated tnoncmier' U))' includes monomers having one epoxy group and one
j !
polytaeri:?able unsaturated bond in a molepule, and it includes, for exarc.ple, silycidyl (meth)acrylate, B-riiethylglycidyl (meth) aery late, 3,4-e;poxyi3y(lohexylmethyi(meth^»ac^late; 3,4-epoxycyclohexylethyl lmet]x)acrylate, 3,4-epoxycyclohexylp;ropyl;(meth)acrylate and allyl slycidyl erJier. They can be used alone or in combination of two or more kinds thereof
The ,^icid group-containing polljrmerizable unsaturated moncmer (c) includes monomers having oiie acid group and one

poly:cieri?.abLe unsaturated bond in a

molecule, and it includes, for

example, polymerizable unsaturatedimonomers having a carboxyl

grouj? sucb MS (meth)acrylio acid, maleic acid, crotonic acid and 6' carboxye thyl acrylate; and pqlymerizable unsaturated monomers havijig ai: least one group selected Irom the group consisting of a
sulfonic acid group, a sulfonate g^'oup, a phosphoric acid group and a phosphate group which are represented by the following formulas**

i I
wherein R^ represents hydiogen or methyl;
I I;
R^ represents an alkylene group having :2 to 4 carbon atoms which may htiva a umbstituent if neqessary preferably ethylene or
propyle0 W represents an alkylene group having 1 to 20 carbon atoms, preferably 2 to 4 carbon atomis which may have a substituent if
aeces'.sarj?; ;
R^ repr^^scmts an alkylene ^roup having 11 to 6 carbon atoms, ipreferably 2 or 3 carbon atones which may have a substituent if
■i 1
nece^isary; j !
R^ represents a monovalent organic group having a saturated or unsaturated alkyl group or ai^ oxyalkylene group which may have a
substituent if necessary; ■I ' ■
X reprtisents a group selected feom the group consisting of a

sulfonic add group, a sulfonate group, a pliosphoric acid group and a
phosphate ;i?roup; , I
n is an ipJeger, preferably ^n integer of 1 to 20; and
n^ is at) integer, preferably Ian integer ofijl to 20.
Capable of being giveri as thd polymerizable unsaturated monomer (d) having an alkyillgTOup navin^' 4 or more carbon atoms
are, ]br ejMmple, ail^l or cyc|oaikyl!(methlacrylate such as n-butyl
[I ' i'
(meth)ac:t:yla.te, i"butyl (metl:i)acrylate, tert-butyl (methjacrylate, n hexyl (m(i:ih)acryiate, octyl (iiieth)ac[rylate^ 2-ethylhexyl (met;ii)ac.ryiiite, nonyl (meth)^crylate, trid^cyl (meth)acrylate, lauryl
(met;ti)ac:[:yl!iLte, Cis-a-lkyl (meth)acrylate s\ich as stearyl
(met;a)ac;i:yli;ite and "Iso Steajjyl Acrylate*' ftrade name, manufactured
by Osak^i. C^'ganic Chemical Co., Ltd); cyclbhexyl (meth)acrylate.
methyicyc to hexyl (meth)acry|ate, tert'butylcyclohexyl (meth)acryiate
and (tyclodicifiecyl (meth)acrylate. T^hey cap. be used alone or in
comtinat]x:»n of two or more idnds thereof ] Among these
polymerizable unsaturated monomers (d)Jsuited are monomers
containiEig as a part thereof, a polynjierizaile unsaturated monomer
having a linear or branched %drocarbon group having 6 or more
carbon atcinis and/or a polymerizable unsaturated monomer having a
cycloaiky] group. | \ !
The {^ther polymematile unsaturated monomer (e) is a
moncmier component which is copolymerixable with the monomers (b),
• ■ 'i ' '
(c) and/or Id.) each described above and includes, for example.
(met]i)acrylates such as methyl (meljh)acrylate, ethyi (meth)acrylate,
n^prc^pyl (]neth)acrylate and ii-propyj (me ttji) aery late; polymerizable
imsaturated monomers ha\lr^g' an isbbornyl group such as isobornyl
(met]i)acrylate. polymerizabl^ unsaturated monomers having an
i3.dan:Lant;Ki group such as adamantyl (metlpacrylate; vinyl aromatic
[lorapouncls such as styrene^ d-methylstyreilne and vinyltoluenel
polyraerLiable unsaturated mjonomers having an alkoxysilyl group
Il j r
^uch aa vinyltrimethoxysilan?, vinylbrieth^xysilane, vinyltris(2-
methoxy*;jthoxy)silane, Y'^^e^acryloyloxypropyl-trimetlioxysilane and y( m
perfluorcoctylethyl (met]^)acr|ylate; polymerizable unsafeuirated
moni)mer5: having a fluoroalliyl group such as fluoroolefin;
polymeri2:;;ible unsaturated monomers having a photopoiymerizable
j, I ■
iiinciional group such as a m^leimi^e group; 1,2,2,6,6-
pentamethylpiperidinyl (metlOacryliate and 2,2,6,6-
tetrtamelliylpiperidinyl (met|i)ac:ryl|ate; vi:ayl compounds such as N-
^dnyJpyn'Ghdone, ethylene, butadiene, chloroprene, vinyl propionate
and vinyl iicetate; nitrogen-c()ntainihg polymerizable unsaturated
monomers such as (meth)acrylonitrile, (meth)acrylamide,
I i
dim€thylaminopropyl(meth)acrylamide, dimethylaminoethyl (meih)ac;iylate and adducts of glycidyl (meth)acrylate and amines; (me1[;h)'acl::ii^li:ites ha\ing a hy I 1
abov^; poiymerixable unsatuijated monomers having a hydroxyl groii]D such as (metlOacrylatejs having a polyoxyethyiene chain having a hydroxyl group at a molecuiar endjl addition reaction products of hydroxyben:i!;ophenones with giycidyjl (metli) aery late such as 2-hydroxy-i(|l"methacryloyloxy-2-hydroxypropoxy)benzophenone, 2-hydroxy-^]t(il'acryloyloxy"2-hydrox3^ropoxy)benzophenone, 2,2'* dihy(lioxy 4 (3-methacryloyl(Djxy-2-hydroxypropoxy)benzophenone, 2,2'-clihy{3ro:>:y-4(3-acx*yloyloxy-2-hyaroxypropoxy)benzophenone, 2,4-dihy(lrox}i)e nzophenone and ^,2\4-tfihydroxybenzophenone; polyroeriieable unsaturated raonome^s having a UV-absorbing t'unctiona.1 group such as 2-(2thydroxy'5'-metliacr>-Ioyloxyethy].phenyDi2H-be;3zotriazo]e; UV-stabiiuing unsaturated monomers such ?is 4'(irleth)acryloyloxy-1,2(2,6,6-pentumethylpiperidine, 4Km^th)acrdoyloxy-2,2,6,6-tetramethyipiperidine, 4"Cyano-4-(m,eth)acryioylamino-2,2,6,6-
j. ;
tetramet]:iylpiperidine, l-(nie|;ti)acryjloyl-4"(meth)acryioylammo-2,2,6,6-teJ;Kimethylpiperidm4 l-(m^th)acryloyi-4-cyano'4-(met]i)acryloylamino-2,2.6.6-tietramethvlDiDGridine. 4*crotonovloxv'

2,2,6,6-tetraniethylpipericiind5 4-crotonoylamino-2,2,6,6-tetramethylpipehdine and l-Grotonpyl-4-crotonoyloxy-2^2,6,6" tetramethylpiperidine; polynaierizable unsaturated monomers having a caibonyl [2 roup such as aorqiein, diacetonacrylamide,
i: I
diac€!tonemf two or more kinds thereof.
Tije water-based fattyiacid-modified acryl resin described
ii :, ■
abov'5 can b^i! obtained by cop^lymerizing the iatty acid (a), the epoxy group'containing polymerizal^le unsaturated monomer (b), the acid groujrcontaining poljnmerizable unsaturated monomer (c) the polymerii^NiiLible unsaturated nibnomeir (d) having an alkyl group having 4 or more carbon atonfs and the other polymerizable unsaturated monomer (e) eac^ described above. A use proportion of the respective component's cajn be set as follows based on the total
amounts of the components (^, (b), (c), (d) and (e):
' ' ■ '
compoaeiii; (a)'. 0.5 to 40 % bylweight, preferably 3 to 37 ?^ by weight
and particularly preferably 7 ito 33 % by weight,
preferably 1.5 to 18.5 % by
component (b)' 0.3 to 20 % bylweigh
v/eig]it and jjarticularly preferably 3.5 to 16.5 % by weight,

lomponent (c): 0.1 to 5 % by 'height,

preferably 0.3 to 4.5 % bv weight

and ])art:icu].arly preferably 0.5 to 4^0% by weight,
compone:[iii; (d): 20 to 95 ^^ by weight preferably 25 to 85 % by weight
and ])art].cularly preferably 30 to 7H\% by weight.
The water-based fattj^ acid-modified acryi resm described
abov3 can suitably be pro(iuced by subjecting the fatty acid (a) and
the epoxy group-containing polymetfizable unsaturated monomer (b)
to addiLtion reaction and then copolymerizing the resulting fatty acid-
modified ipoJynierizabie unsaturated monomer with the acid group-
containing' polymerizable unsaturatjed monomer (c), the
polymerii!;ab le unsaturated monomer (d) ha^4ng an alkyl group
havijig- 4 oof more carbon atoms and the other polymerizable
unsaturated monomer (e)^ !;
Ill jiroducing the fatty acid-modified polymerizable unsaturatiiui monomer described above, the fatty acid (a) is suitably reacted wicb. the epoxy group-containing polymerizable unsaturated monomer '.h) in such a proportion that an equivalent ratio of a carboxyl group in the above fatty acid (a) to an epoxy group in the epoxy group containing polymerizable unsaturated monoraer (b) falls in a rangf! of usually 0.75- 1 to 1.25!"- 1, preferably 0.8 : 1 to L2 ■ 1.
Thd fatty acid (a) can be reacted with the epoxy group-containirLs; polymerizable uj^^aturated monomer (b) in the presence of a polymerization inhibitor described later according to a conventional method on such conditions that a carboxyl group in the fatty acid comf oneni: can smoothly be reactedlwith an epoxy group in the epoxy grou]rconta.i.ning polymeriziable unsaturated monomer without bringing about problems on reaction such as gelation. They are suitably re£i'?.ted on the condition that they are heated usually at about 101] to about 180'C for about (|).5 to about 10 hours.
In tMs reaction, capable of b^ing used is, for example, an esterificatic)];! catalyst including tertjiary amine such as N^N-dimethylaminoethanol arid a quateijiiary arnnionium salt such as tetraethylammonium bromide and tjetrabutylammonium bromide, and an orEraiiic solvent which is inett to the reaction may be present,
The polymerization inhibitor jdescribed above includes, for example, publicly known radical poltymerization inhibitors including

hydioxy compounds such;as hydroq|umone, hydroquinone
mon-3mei;hyI ether, pyrocatecioi and p"tert-biitylpyrocatechol; nitro
compounds such as nitrobenzene, nitrobenzoic acid, o% ni or p-
■' I'
dinitrobenzene, 2,4"dinitrotoliiene, 2,4-dinitrophenol, trinitrobenzene and picric a::id; quinone compoundsilsuch as p"benzoquinone, dichJorobiEiiL^soquinone, chloi^oanil, a||ithraquinone and
pher.antJiroquinone; and aitr I I ■'
and :aitro3o-6-naphthol. Theiy can be used alone or in combination of
two or more kinds thereof, i 11
' I i I
The \vatei-based fatty acid-modified acryl resin can be produced, far example, by sulxjecting the fatty acid-modiSed polyinerissiitile unsaturated rapnomer obtained in the manner described above to solution pdlymerization with the acid group-contaming- polymerizableuns^turalied monomer (c), the polyinerij:;i;ible unsaturateid mj^noraer (d) having an alkyl group having: 4 rjt more carbon atojnjs and;the other polymerizabie unsaturar.eii monomer (e) in ain organic solvent in the presence of a polymeri:2;at!ion initiator.
In leiiipect to the use proportions of the respective monomers
based on th€;t total am.ouni of tjhe monomers, that of the fatly acid-
modified polymerizabie unsat|irate(| monomer is 0.8 to 60 % by
sveight, pjreftjrably 4.5 to 55.5 % by weight and particularly preferably
10.5 to 49,5 % by weight; that| of the; monomer (c) is O.I to 5 % by
weiglit, preferably 0.3 to 4.5^ by weight and particularly preferably
0.5 to 4.0 % by weight; and th^ of the monomer (d) is 20 to 95 % by
weig^tit, preferably 25 to 85 % jay weight and particularly preterably
30 to 75% by weight | |:
The polymerizabl^iunsJEttufated monomer (d) having an alkyl grou]) haviing 4 or more carbon atoms described above preferably
contsiins, BS described abOvi:!,lthe polymerizabie unsaturated
-' i '■ ■ monc^mer liaving a linear or bf anch^d hydrocarbon group having 6 or
more carl:ion atoms at least as a par| thereof from the vfewpoints of a
watev res]>stance of the coatm| film jformed and a production stability
of th(i water based fatty acid-ihodifi^d acryl resin- Capable of being
?ivei; as the polymerizabie unsaturated monomer having a linear or

I I'l ' f I
branched bj^drocarbon group fiayiin^ 6 qr more carbon atoms are, for example, n-bexyl (meth)acrylW; octyl(!meth)acrylate, 2-ethylhexyl (meth)acryl;;:Lte, nonyl (meth)^cryiat;e, tifidecyl (meth)acrj^late, lauryl (methl'acrylate, Cis^aliyl (B:iel[b)a€rylate siich as stearyl (meth)acryi;;;ite and "Isostearyil Acrjrlatef (trade name, manufactured by Osaka Organic Chemical dciiLtji.). | They can be used alone or in combinai;Li>i:i of two or more l^nds tl|terep£ The polymerizable unsaturjited ni.onomer havingj an alkyl group having 6 or more carbon atoix.s is used preferahly in a ^angepf I'to 30 % by weight, preferably 3 to 127 % hy weight and more!preferably 5 to 24 % by wei^jht based on the total a,rnount of the components: (a),|(b), (c), (d) and (e).
The polymerizable unsiaturated ^onomer (d) having an alkyl group having 4 or more carboii atoniis preferably contains, as desci'ibed above, the polymerijzable itins^turated monomer having a
111: I
cycloalkyi iproup at least as a part therejof, Use of the above monomer makes it possible toielievate afweatherability and a water
! i ;■ i
resistance of the coating film, formed. Capable of being given as the
polymeri2;iible unsaturated monomer having a cycloalkyl group are,
for examipie; cyclohexyl (metWacirylate, fmethjrlcyclohexyl
(meth)ac:ry]ate, t-butylcyclohexyl (njeth) aery late and cyclododecyl
(metWacirylate, and they caa i^e used alone or in combination of tw^o
or more kinds ihereof^ The pioiymerizaible unsaturated monomer
having a cycloalkyl group is used suitably in a range of 10 % by
weight or more, preferably 20
to 60 \yo by weight and more preferably
25 to 45 % by weight based on the tptaljamount of the components (a),
(b), (c), (d)and(e). I M
The other polymerizable u;[isatuijated monomer (e) preferably
contains at least as a part theireof, alcartoonyl group-containing
polyiQeri:?able unsaturated monbmeir as! a copolymerization
eomiponem:* The carbonyl group-contailning polymerizable
f 1^ i \ unsaturated monomer includes, for exainpie, acrolein,
diacetomtcrylamide, diac^tonemethacrylamide, acetoacetoxyethyl
■' i i |i j
methacrjlate, formj^bstyrbl and Vlinyfl alkyl ketones having 4 to 7 carbc»n atoms (for example, vinyl methyj ketone, vinyl ethyl ketone and vinyl butyl ketone). They can be uased alone or in combination of

I ■ :
two cr more kinds thereof.!
Use of the monomer containibglfl le carbonyl group containing
ipolyraerisiiable unsaturated monomer!alg the other polymerizable
■' ' i . '
imBaturated monomer (e) nmkes it Jfossible to promote auxiliary
cross-linkittg of the above learboii^l grod) with a hydrazine derivative
desciibed lai;er in addition to oxiaatibri uring by the fatty acid (a)
component by using in combination wita the above hydrasiine
derivativ:: and makes it possibleito e*lev|te fus^ther more a gas^barrier
ipropijrty of the coating film and obtain). coating material providing a
rioatiag film which is excellent in physicbl properties such as a
vveatherabil:i.ty and a water resistance. In this case, semi-drying oil
fatt5^ acicl^^ and/or non-drying: oUfatty adids each having a low
oxids.tion curing property can be! used al the fatty acid (a).
The- sibove carbonyl group-cohtaiining polymerizable
Linsaturated monora.er is used suitably m a range of 0-5 to 35 % by
vsreight, pi^-^ferably 1 to 30 % by weiglit |nd more preferably 2 to 20 %
by weight bELsed on the total amriunt of |he components (a), (b), (c), (d)
:md (e). I ;;:
The Cither polymerizable unsatiijijated monomer (e) preferably :ont£.ins a vinyl aromatic compound^ at ] east as a part thereof. This makes it po::;sible to enhance a copol^Tuirizmg property between the cQonc^merij and provide the resulting fatl ly acid-modified acryl resin ;^v"ith a water resistance. The above viiBjd aromatic compound is used suitably irj a range of 1 to'50 % by w^ig| t, preferably 5 to 45 % by
j: l| ! I I
vreight and more preferably 12 to 35 % I y weight based on the total -imotint of the components (a), (b), C^)' ( Ttie ^«i/ater-based fatty aci^'mlpdified acryl resin described i3,bove can be produced by dispersing th€ mixture of all the polytaerii^able unsaturated moncim^rs dstscribed above in an aqueous mediam sso that an average particle |(iiiameter falls in a range of 500 nm or less^ for example. 50 to 500 n^, mrticularly 75 to 400 nm and more particularly 100 to 250 nmi;and,th|n polymerizing them.
Further, the water-based Ifatiy acid-modified acryl resin described above can be prcducedj'as [wellby a method in which all the polyrierizable unsaturated monomers qpscribed above are

copolymeirii^ied in an organic solvbntiiandin which the resulting copolymer is- neutralized by a neiitr^iiziag agent to be solubilized in water or rlLsipersed in water, a:method in which this is fiirther dispersed ax an aqueous medium byijmqans of a disperser having a high energy shearing ability and a metnod in which all the polymeri:gable unsaturated mon TlHi' water-based fatty acid"niodi|ied acryl resin described
■ \- - ' i above ha!? pi'eferably a weight average molecular weight falling in a
rangi? of ii^iually 10.000 t6 500,000, pkrlcularly 30,000 to 200,000,
If the abt:ive resin has a weight average: molecular weight of less than
10,000, tlie finally obtained coating fiilni is reduced in a
weatherai:iiiity and a water resistance is a certain case. On the
r' ll,
other hand, if it exceeds 500,000i thelpapticle of the above resin is redu(!ed in a fihn-forming property, and! the coating film formed by the water-based coating material is red) iced in a barrier property in a certain ca^-e In this case, the weight siyerage molecular weight is a valu€i obtaiiied by reducing a niolecw^r weight measured bv gel permeatiijn .::;hromatograp|hy using tetra hydrofuran as a solvent based on a molecular weight of pbiy^tyrine, "TSK gel G-4000H x L", TSK: gel C; lliOOOH x ]J\ ^^TSK gel GJiasq OH X L" and "TSK gel G-2000H X L" \all manufactured by Togo Ci p,, Ltd.) can be given as a column UEied for the above gel pesrm|ati )xidation curing property is exceeds 40 %, the coating
Qlm ibrmEsd becomes hard and' fragilbi wttth the passage of time in a iry s bate ^3 nd it is inferior! in pbrfciri^an|es such as a weatherability
The water-based fatty aeid-niddiiied acryl resin described above has preferably an oil leiigtih fisjilni in a range of 0.5 to 40 %, particularly 3 to 37 % and moie part|icu| ariy 7 to 33 %. In the present specification, the bil length is a! }roportion of a weight of the fatty acid to a weight of tlie resin sojiid matter. If the above resin bias an oil length of less than 0.5[%, the insavisfactoi'y. On the other ha!n.d,|ii!f i^

and an alkali resistance, ;
The water-based coating nia^^riall (II) used for the method of the present invention comprisesithdiwaterhased fatty acid-modified acryl resin described abDve as ^ basfe^re^ in, and it further comprises preferably a hydraxine (.erivatiivb in addition thereto. To be specific, the above derivative inc udes, for exiamjle. saturated carboxyhc acid dihydrazide having 2 to 18 carbOn aiitomn such as oxahc acid
' ii'! ' ' j
dihydrazide, malonic ac:d dihyflraziide, |:lutaric acid dihydrazide, succinic acid dihydrazide, adipjc: acid:dihydrazide and sebacic acid dihydrazide monoolefinlc unsdtiirated clcarboxylic acid dihydrazide such as nii!ib;::ic acid dihy|drazidB/fumarifi acid dihydrazide and itacomc a:id. dihydrazide; phtl^lic acid dihydrazide, terephthalic acid dihydrazide or isophthaic acidldihyidraside, dihydrazide,
A: I, ii I.
fcrihydrazide or tetrahydrazidefof pyromeRitic acid;
nitrilotrihvdrazide; citrqyl trihvdrazide, 1,2,4-benzenetrihydrazide,

ethy]enedra]ninetet:L'a.cei;ic acid|;t!etrahydrazide, l,4,53'iiaphtic acid tetrahvdraz:ide; polyhyd:azide .obtained by reacting a low polymer having a ciiboxylic acid lower alkylester group with hydrazine or hydrazint^ hj/drate; comeoundsj having a hydrazide group such as carbcmoyi dihydrazide; lissemlisarbazidc; dixsocyanates such as tLexamethylimediisocyar ate anid|i3oi}hori)nediisocyanate and multifunctional semicar )azide| Obt^ibec^ by reacting polyisocyanate aompouncLs derived fifon: the alfc^e Aiiso ^yanates with N.N-sabstituted livdrazines £ lich aai]l|?,Nf}dimiethylhydrazine*and the
; p ' ' ;i i
bydrazid hydropMiic j^roup such asi polyM aijld pc lyethyiene glycol monoalkyl
' II ■ ■ I' i others; cctiipounds having a semica^bazide group such a.ti mixtures of
the above maltifunctional! semfjarb^zides and the above aqueous rnultj-fiinctional semicarpazidellanci compounds having a hydrazone
roup such as bisacetyldihydra|2Qrie^j
Addition of the hydraaiii^deifiiyatives described above to the
i Iii

!hyde|iaiidj[therbfore they are usseful When •mocfifiedj^cry I resin has a carbonyl group, ing ;jigen]t ifor i iuxiliary cross-linking, of the'lhyi^azme derivatives described
I'll' h '
rangpiotO.Ollio 10 % by weight, Veigiit, ' :■ ; ' ■
ifcing matei*iaJ (II) contains preferably at K\ fjCQta the group consisting of nitrites,
aicesj and poly imine compounds. The le, spdium nife'ite. calcium nitrite, bitritie andi am monium nitrite. The pie, sodium pliytate and potassium
water-bailed coating maiippal (P) mlkkesi! it possible to allow the coatiag film formed to a|pprb a^id removp harmful substances in the air, for es:ample, formal the Mi-ater based fati:y a they can aci: as a cross-1]
A blending amou: abovi? falls preferably in particularly 0.1 to 5 % b^
clud^, Ifbrilqxariple, sodium tannate and
■ 1 i !
1 ] .' i ■■
potassmrri t^innate. Ths polyi^liiind compounds include, for example,
N-{2-hvd]:ox'i^ethyO-ethp mediaiminetria^ietic acid (HEDT^O,
athylenecli;iinine-tetraac|||tic adid (jEDTAi
diiethylenediaminepentafflcetic ^cid (DTP^,
propj.4enfM;l:ta:minetetraa »|tic ai|ad (pbTAj), iminodiacetic acid,
nitrilotriacetic acid (NT
iiethylene triaminepent
alkaline metal salts the
by intercalaring monoa
ammonium ions into str
combination of two or tiMk kiriclfe tilereol.
ethyleiieiihosi phonic acid (DTPMP) and £ aiidiintercajation compounds obtained lamitEiesw polyammes and quaternary jiediphosphalios such as aluminum te. flThevlcan be used alone or in
dditionof the a prev€!nt rusts generated surface of a cioating film (n) to produce dotted ru 2oati)ig film formed by ti reach the coating film fo 'ID. An ad The water-based least one coinpound sele phytates, taanates, phos ciitriteii i]]<:lij.de for exa a:itrite barivi phytates include ex phytate. the tannates> ve b£[sic;comp(3unds makes it possible to m allmetai fat e from bleeding onto the
rmed] by the waterbased coating material evettif the rdsts generated pass through a watdir-liased i nder coating material (I) t-o ed bjr;ltfae wat srbased coating: juaterial
0.02|!t6 2 % by weight, preferably 0.05 to
I- I '
of thelbasic cpacipounds described above

water-based coating
lie vi^eignt 61 tii€
ating ioctaierial (II) used for the method of ains aipigmen; in a pigment volume {'and tirdferablt' contains it in a pigment g inia raihge (f particularly 10 to 35 %, 30%. I llf the pigment volume concentration Lg .fili^ for;med is unsatisfactory in a hiding !0n tlije other hand, if it exceeds 45 %, the l^ced m k finisl ing property as well as a mcaSeJ: I'
i h !;
tyen aiSithe pigment which can be blended ing material (ID are, for example, color
whiie anti red iron oxide! extender carbqnfite^, magnesium silicate hydrate, ; and rust prolective pigments such as the
i ■ I i'
ents described above.
ating nlat^ria] (II; described above can
catalyst for accelerating oxidation curing.
1 % by wi^ight based on material (II),
The waterbased the present invention co concentratiun of 5 to 45 volume concentration fa farther particularly 14 ia less thjii.n 5 %, the coa power in n. Cijrtain case, coating fi].m formed is r barrier p:r'operty in a ce
Capable of being with the (iva'cerbased co pigments such as titani pigments sr-uch as calciu talc, mica, clay and bar phosiphoric acid base pig
tludesi, for fexample, salts of acids with at :om the grdup consisting of aluminum,
i The vi'ater-based 2ont£in a incital dryer as The abovB iiLetal dr;;^er i least one OIIE tal selected calcium, cerium, cobalt, jiton, Hthiium, mignesmm, manganese, zinc, and 2;irconium, and the move acids jincliide, for example, capric acid, i^apryhc acid, ijsodecanoiiacid, linolenic acid, naphthenic acid, aeodecanoic acid, octeic ieid, olfeic afcid, palmitic acid, resiin acid, cicinoHc acid, soybean oi|fe.tty iGij The water-based contain a co]rnbination o: coating matc^rial includi soluble or emulsion type fluororesina. epoxy resi surface controlling agen dispersants, surfactants aids, antiijeptic agents,
(II) described above can hoseiiiita^ly selected from additives for a
resii^ foir mollification such as water icrjrl resins, all yd resins, silicon resins,
uretliaheljresiis and polyester resins, [■ UV Absorbers, TJV stabilizers, pigment
efoammglagents, tliickeners, Iilm-forming
\-\ \:
ti-mojdlk^ents, antifreezing agents, pH

:oiitio.llirig agents, llashliust unlitibitors, aldehyae scavengers,

■ I ■ ,! jj ,1
stratified clay minerals,
Howderbrfine particle activated carbons, photocat*»]ysi:t titanium diiide adcj. cwntamination-reducing agents
11: iiii ■ [! {j !
such as polyalkylene g]yip-m6(ppea alky^
The viraterbased fcatingimaterial ](II) described above is
excellent in a gas-barriei|propejfty of theicoatmg film formed, and to
jj.' j 'i ,j ' j,
less. In ::be present sp« accoidini:; to JIS Z 0208. anhvdroi:is ciilcium chlo
be spe(!ifi [afication/ttie permeability can be measured |ii To be specific, an optimum amount of le is ptit into a vessel, and a test coating film :is ad:ne:::ed to an apiifture tf^rt of the vessel by means of a sealing v/ax agent to prepare a llest matter for meeisurmg a water vapor perrjoeabi iity. This test|iatteius left standing still on the conditions of a temp-2riEiture of 40T jand a ^relative humidity of 95 ± 2 % for 24 hours to measure a chailge in the weight thereof, whereby a mass of water vap'i:»r permeatlnglMJer m^ of the test coating lilm is calculated. Used as tbe test coatingillm is a freie coatini? film having no pin holes obtained hj coating the |ifatingl material'on a mold releasing paper by
means of e film applicatii!ir or aiJL air spray so that a dried film
thickness s 40 to 50 ij.m|t,| prefarably controlled to nece^us ar;^ by means of The drying (::ondition is
'-■' . i! 'i ■ In coating, the coating material is
Iviscosity of 80 !KU or more and defoamed, if
*ie:foaming!jmacliine, and then it is coated,
days on the conditions of a temperature of
20'C and a relative humliitllity of 60 %. The drying condition until the
test after coating is 2 w^jeks at kitempera^ture of 20 to 25'C and a
relative humidity of 75 wtRH oriles^. The water-basedferoatingimatierialiOl) described above is
latter concentration of the coating material
% by; ;^ei^ht, pireferably 40 to 60 % by
Hi solthaia cobiting amount per one coatins
Jo kg/in^,ljprefe^ably 0.08 to 0,3 kg/m^ and
kg/mf^ll ■■ \\ !! : ! 'j ■ ' J! ■ 2arrip^ oat byjineans of a coating
f, an'ab sipray• jan airless spray> a hthin

gun, a urixv<:rsal gun an brush and the coating is carried out> IjroUer, an air spray, an airless spray, a lithin m ord^r tollobtain the high finish, curedlysuially fpit* 2 to 24 hours at about
preferably by means of anun and \3. universal gu
The coating film \^
The i)resent inve^|ion si^U inore speciifically be explained below wiiih. i:eference to jitamples. j'Tarts" and"%" are "parts by weight" and"% by weigliif'. Productioii of fatty acid- \t^odified polvmenzable unsaturated
Production Example 1 ThB ibllowing co:
jonieiits w^re piit into a reactor and reacted
I . I.; ■ i '1 ! ■
it a jreac^:io:t:i temperature of hmC v^hile iStirring to obtain a fatty

i' 1). The "reaction of the epoxy group with fonitOTed b^ measuring an amount of the
acid"n::i odife d mono m.e r
the carbcuijri group was
remsining" carbonyl groi^b. Abbiit 5 hours were required until the reaction ^vain completed.
Saffiov/er oil fatty aci|
Glycidyl methacrylat Producti Linseed oil fatty acid
Glycid;^ 1 laiethacrylatt
280 parts 142 p^rts
'■ i ■ I ■
ed raonomjer (a^2) was obtained in the same Exam;pie 11, except that the components to jiis shown |elow^: ^80 parts i42 parts Producticn ^Example 3
manner as in Productio be reacted were change Coconut oil fatty acid Glycid}! itiethacrylat Productic n of water-bas Production Example 4
Afatty acid-modified md^nomler (a-^3) was obtained in the same
lExaraiile Ij, exdept that the components to l^s shown Ijielowj ;
210 parts
ti ' ^' 142 parts
111 'i ' !' ^
fatt'VJifeicia'modifLed acrvl resin

The following coi3y|onents were piit into a glass beaker and
3tirr6!d at 2000 rpm for 1| minutes fcy means of a disper to produce a
prelunin^iry emulsion, alpl. theii this preliminary emulsion was
ubjected w high pressu c^ treatment at llOO MPa by means of a high
■ ' i I
pressure emulsifying appliratus in which la high pressure energy was
applied t(j allow fluids t
emulsion ha'/ing an ave
MonoDiei' ■iiiinul-sion com Fatty acicl-modified m n-Butyl iiiiethacrylate i-Biu.tyi inethacrjdate 2-Ethylh(!xyi methacry Methaci^^'li::: acid n-0ctyl-3~:tnercaptopro^ "Newcol 707Sr (remai Deioniz^d water
Collide witii ekcti other, whereby a monomer
' ■ I' ■ icl^ diaiheter of 190 nm was
sitiori i mer (a-1)^
I !■
N(?>:t, the monomMa: emulsion desuiiucd above was transferred Q a flask and diluted wim deioniaed wat6r so that a solid matter
■ Then, the temperature was elevated up to 55T': and an initiator aqjlteous solution prepared by dissolving 2 g of 'VA-()86" (remark 2) in and s tirr(?d for 3 hours Then, an initiator aque ^VA-()86" (remark 2) in stirred for one hour whi
30 parts 25 parts 27 parts 17 parts 1 part 0.5 part 10 parts 85 parts
g* of deionized iv^rater was added to the flask ie mkintaining the above temperature. j5 solujtionjprepaired by dissolving 0.5 g of g of 4eiomzed ^ater was added thereto and mgunjtaining tlkje above temperature, and the solution was then cocled dojw^n to 40 'P and controlled to a pH of 8,0 with dJmethylarninoefehanol to obtairia v/aterbased fatty acid-modified acryl resin (la||ia\ingia sphd matter concentration of 40 % 3.nd. £Ln ai/'enage particle Hiamet^x ofi 185 lim.
(Remark 1)'Newcol 7071 Bjmulsifier Co., Ltd., a:
""■ tride iiame;|maiuvfacturedi by Nippon
ioniuiii I 't'
polycr/etiiyienealkylbeii Jenesulfonate, active ingredient: 30 % (Remark 2) "VA-086": tri|e naiiie, nianufectured by Wako Pure Chemical Industries, LtH|: 2,2'-|Lzobis[2-methyl-N-(2-hydroxyethyD

Producticin l?]xamples 5 liS

obtained m :;he same m that the i5i.onorner comp Productkio likample 9
A lour neck flask reflux tube {-md an inert
W:3it(?irbased fattjfl^cid-akiidified aqryl resins U-2) to (1-5) were
ner as mProdulction Example 4, except ition wks bhanged as described in Table 1.
I : 260 parts
' 150 parts
I I I 86 partfs
I i 86 parts
ill 90 parts
I II 28 parts
I ; !; 2.1 parts
ened'lat 120"C for 2 hours to obtain a brown,
ftwipped witH a stirrer, a thermometer, a s'intii'oducing tube was charged with 500 parts of "S'wazol 310" (rdliark 3) and heated up to 120T. virhile allo^^ing nibi'ogen gas to{|ass through under stirring. Then, dropwise Etdded in 3 houfi!^ whilb maintaining the temperature at 120°{y wm a mixture of^ fatty aci.d-modified moi||m,er (a-l)
n-butyl [iieithacrylate
i-butyl niethacrylate
2-eth3/lhia^:xyl acrylate
'TBAS-Q' (remark 4)
azobisis obit tyronitrile
Then., thti sdlution was
tramsparr-nt fatty acid'nilidifiedl acryl resin solution having a non
volatile miiitter content y 1 Ij j I'
Petroleujn Co., Ltd., miiwal spirit 11
(Remark 4) "TBAS-Q': tl|tde n4me, Imamifactured by MRC Unitec Co., Ltd., com prL'sing a compljund represented by the following formula as a principal component-
CH2=CH-Tlie liatty acid*m* was i3ubj •Nll-CiCH3)irCH:2"S03H. fied ^cryl resiri solution described above
iressiire treatment to remove the solvent,
and 10.9 g of triethyla g of the resin which wa
f^e as a neutralizing agent was added to 875
eontroiled to a non-volatile matter content of
n i i ' ■ 80 %. Then, the mixtui:| v/as stirred at a; high speed Wliile gradually
addiiig 700 ig of deionizel[|water to be preliminarily emulsified, and the above preliminary e|:|ulsioa was subjected to high pressure

treatment at a high preMJure ofiiiJOlMPa |by means of a high pressure
smulsifyiiiis^ apparatus iijwhich^^ high priessure energy was applied

jith esjcji otlier, i A water-based fatty acid-averaige particle diame ter of 200
ntent df[44 % jwas obtained by repeating
I resiii 1(1-7) wa^ obtained in the same Sxamfalj? 4, excejpt that the monomer
to allow fliiiiis to colUde raodified acryl resin (I"6: rim and &. solid matter c twice the above pass. Production Example 10 A water-based ac manner as in Productio
compositicn was changeff as descHbied in ITable 1.
Production Example 11 i; j : ! : i
A ^vater-based faiiy acid*-n;LO(iified 'acryl resin (1-8) having an
If ;' ■'■,'■ I
14 i I
average particle diamet||! of 630 iim was Obtained in the same blend
l[\ ■■!■;: ] ^
comF>osition and proced\a{i!e as iji production Example 3, except that
in PioducticiQ Example f^jthe resulting pteliminary emulsion was
stirred ai: 10000 rpm foil H minutes by mdans of a disperser having a
high sheiiii'ing ability to ptain jamdnornqr emulsion having an
average i] article diamet^il of 52D'link. j '
Ml' f"' ^ ' ■
Tliii monomer co|jtaositipris and tii^e property values of the respective? fiitty acid-mopnfied E^ci|yi^resin^ axe shown in Table 1.

Table 1

'±x/ f'\i

Production Exampte
4 5 6 7 8 9 10 11
M 1-2 1-3 1-4 1-5 1-6 1-7 1-8
Fatty acid-modified monomer la-l) 30 260 30
Fatty acid-modified mdnodier(ja-^ : :: AS: -30.ia- aais:- . - --

Fatty acid-modified monomer {a-3) 33.3
Stvjrene _ . ... „ „ 15 - 15-.. 15 15 _ „a50— _. ___ \—

rtp* M\ r^ V—^ - Rft op 9^
Tu^i:yuiyx^jiieirXiac^^ia:if6 r - rr Zt'O Xyj - - 7 -.- - -_ - T — ■-.-.' -.-.- .- - ou r^O.O , Au ~
i-Butyl meih^ryTsie " 27 5 20:35 24.7 ^ 86 "35 22
t"Bxityl methacrylate 20 10.35

- nyuTuikyfShiLyi ixuKJfxnhts . •^ ... —.-.—_- —^—r—— *k^UL *t*u ■ r,- ■ 7^, - ■■ -.^^—,—
2-Ethvlhexvl methacrvlate 17 19 8 8 20 90 29 17
Diacetonacrj'^lamide 5 5 5
Methacrylic acid 1 ] 2 9 2 1 1
Cyclohexyl methacrylate 30
i 'TBAS-Q' (remark 4) -^'> ",'M.£--!._. j 1
i n-Octyl-3-mercaptopropionate 0.5 0.5 0.3JLl^CrxXAJLl. 0.3 0.5 0.5
1 Qn»»r* 1 nn^^^
Acid value 6-5 6.5_ 13 13 13... .. , 10.8 6.5 6.5. _ . )
:\y /M j "t^jj-w J

Production of water base I coatjrigr riiaterijal
Production ISxamples 12 » 21' ■ ; | I
A vessel was chai ed in bolder witli the respective components
shown in (vCmposition Q\ of HafeIp 2^ andjthe mixture was continued
to be stincid for 30 minul js by inea^s of $ disper until it became
re>sp(ictivo components s!||own ii. added in order to the ab resp(?ctive ^^^ater-basedq pence abilities of coating
homogenfious to obtam tjje resfJejctiYe pigment pastes. Then, the
Composition (B) of Table 2 were ^e resp^btijve pigxaent pastes to obtain the ating Iniaterialsl The water vapor ilms folcmed by ithe respective coating
materials; and the propei|fy values of the ^bove coating materials are
shown in Table 2.

CRemark5)"Sraoff72N"^ Yakuhin Go., Ltd., antis (Remark & "Nopcosant Co., ]jtd.. pigment dispe (Remark 7)' Adekanol Co., Ltd., thickener (Rercark S) "Titanium Tayca Corpcration, titail (Remark 'i) "LF Bosei P
trade jaan^e, manufactured by Takeda
tic at^ei^t i
'; trade Iriaine, manufactured bv Sun Nopco
j I I ' ! '

ant '1 i; 11 ; 438't trade name, manufactured by Adeka
i i I
ite J^-6d5"" trade name, mamifactured by am wiitie, ^specifib gravity: 4,1 ■2" ^ tirade name J manufactured by Kikuchi hate base l-ust preventive pigment, specific
^^ravi-ty: 3.5 {jl :
(Rertiark 1.0) "Sunlight SiL-SOO'^ trade name, manufactured by
Takehara Cliemical Co.,|l(Ltd., cklcium carbonate, specific gravity^ 2,7
(Remark 11) "SN DefoaijijEjr 38CJ":|trade name, manufactured by Sun
Nopco Co.; Ltd., defoamij|ig agetit
(Remark 12) "DICNATEi'bir'^trade name, manufactured by
Dainippon Ink & Cliemik^kls lnc-,jmetal dryer
J S ' ' I
Water vapor permeabilio* m.eafeuijed according to a method described
inJtszomB i;i ^ :i
Production of water-basefi iindfer coating material
Producti(]n JSxampies 22i!ito 24 \ \ A vesisel was chaii^d inbijder with the respective components sho^\n in Ccimposition (Q of Talblid 3, and the mixture was continued to be stirred for 30 minujies by means of a disper until it became
ill ^ IM
homogeneous to obtain jfi i \\ i.
\'i i I i ^'
pigrc.ent pafites. Then,
le resipective components shown in Composition (C) of Tabl6}|3 wer^ added in order to the above pigment pastes to produce the reflective 'ivtalterbased under coating materials A to C.

I Iff Mi '
(Reiaark 13) "Red Iron Olkide N!^ 5^"'-trade iname, manufactured by
Nihon BengBiR Co., Lt4i|red Drbn! oxide, specific gravity: 5.1
(ReiiQ.ark 14)' 'K-WHITEj|4aWt tirade nanie, manufactured by Tayca
CorpDrati: n, aluminum y:ipcdydihydrogen^hosphate, specific gravity'-
.11 ,,, I
l. \ ' I AZ-5116"!: trade riame, manufactured by
DSM Resin Co., Ltd., solil :m.at|er;content:50 % waterbased alkyd
ijfij i j resin, solid matter conteit: 50 % !
(Rercark 16) "38 % Resylol AY-isew/SSW^": trade name,
manufactared by Soliitia|Co., iJtd. acryl-ufiodfified long oil water-
base Preparation of test coatel plate 11 ; I
Exaaapleis 1 to 9 and Comparaltive JExampljes 1 to 4
A areel plate (15(|| 70 xlo]$ mm) p][escribed in JIS K 5410

relative humidity of 60 m having a vvhicli wa.!5 defatted witWilcyiene was used gis a substrate. Each vrate r'ba!3 for a dajV tp provide an under coating film em of 30 rim. Tlhen, each wateirbase coating nuiti^'.rial shownjii Table 4'which Was diluted to about 70 KU vi^dth clean water was cdailed thereon by a brush so that a coating amount vvLis 100 g/m-, a|i|ll each waterbas^d coating material was further cciabiijd thereon ifter 4 hou|:s so that a costing amount wauS too g/ra^. Then, it wasi,aried oh the conditions of an air temperature of 20'C aril a relative hufoidity of i60 % for 7 days to form an upper
i 111; ' ■ i I
I ■ ' '
coatiag fiJ.m. having a dri(|d £Jm thickness pf 60 nm by the coating material, ^v^:l.ereby each t|st coated plate was prepared. The
tespecirivi:! t(;!St coated plates thus; Obtained v/ere subjected to the following te^iits. The rPRilts thereof are shown in Table 4,

'■"l) IJuild fciiL'ling: each ^|itBrb|SfiCl coating material was coated, and
nil I ■ ■" 1 ' i '
i;hen the coating film api||aranc|e Iwafe visually evaluated one day later after d:ded-
©' particulaiiy esl ellenlijiu!t>iiild fefeLing
o; excellent in biiicL feelllngl ;
x: poor in build Miling! ii | i ;
V*2) (jlossiictess (60 degrii igloss|: fche test ciDated plates were
measured according to aji^Ht method of a lielative-specular glossiness
iprescxibed m JIS K 560«-7 i i j M I
(*3) (3orxC'Sion resistances!! tiie wiiaterbasedjcoating material was
! is '^ ' ^ ■ ^ coated and then dried oii^itthe coliditions of kn air temperature of 20'C
and a relacr-'e humidity lip 60 mf 5ubj6:cted to a combinedilycle corrosion reaistance test prescribed in
ns K 56:ii; I. :i.n 36 cycles t| evaluate the surface of the coating film
jjj) i| ] I !
accordlnixf to the following cxiteijia' ■■
Jff ■' 1 i i
O: no nists are oq|en/ediiO!a the coating film
jijj . '^'- \\ ' i
Oiy- rusts are observed hti & very small part of the coating film
'i 'f' I ' '
£^'^ rusts are obse|yed ois a part of the coating film
I SfW 1 ■ '
X : rusts are obselved on the whoieiface of the coating film (*4) Accelfirjited weatheilkbilityl tlie respective test coated plates were
Ml! i! I i * ; , *
irradiated for 1000 hours accordijag to an accelerated weatherability test j^rescrilied in 9. 8. ij [sunshine carbon iarc lamp method) of JIS K 5400, an ¥ iii ' '
to a chal]=:irLg degree prejicribedljIinlS. 6 of JjlS K 5400. The lower poinc show? that the ch8||king ||ro|jeeds more.

What is claimed is:
1. A coating finishing j|ftei:liod|i comprising coating a water-based
under coating material (l on 4 interface of a m(3tai substrate or an old
:oat(3d face of a metal sxi,fe:fatd|a!cjd then coating on a coated surface
thereof, a water-based ciiiting: ilkallerial (II) comprising a water-based
fatty acid modified acrylleain as 'i b'?ise resin component, wherein
i' ' i f I I ' '
Dhe iibove Wiiter^based cdatirAg material UI) contains a pigment in a pigment ^■olvlme concentration Miling in a range of 5 to 45 %. and the abovo wator-based fatty lcid-ni|dified acryl resin has a form of a fine particle having an average particle diameter failing in a range of 50 to 500 nm,
2. The method as desc||tibed;I|L Claim i, wnerein the water-based
under coistiiiig materials contains a phosphoric acid ba£ie pigment.
i Mji i i
i !■- ■
3. The mii'thod as desc|ibedi|i plaim 1 or 2, wherein the water'
baseii fatr.y acid-modifieJacrylNain is a resin comprising a
'I ' T ■ I '
structural unit derived abm a fetty acid (a), an epoxy group-containing polvmerizabll unsatiurated monomer (b), an acid group-containing polymerizabl|| unsailurated monomer (c), a polymerizable unsatura ted monomer (c| haviiig| an alkyl group having 4 or more carbon ai:on:ts and the otler polynierizable unsaturated monomer (e).
4. The method as described li IcJlaim 3, wherein the polymerizable
'if il ' I
unsaturated monomer (tf haviis an alkyl group having 4 or more carbon atoms contains a polynilriisable unsaturated monomer having a linear or branched hyc§ocarbpn ;group having 6 or more carbon atoirts..
5. The m polymerizable unsaturated mbnorjier (d) ha^/ing an alkyl group
having 4 or more carbon* atoms|co}itains a polymerizable unsaturated
monomer having a cyclo|U^yl'gro!iip]

3. The Diediod as desc| ibod iiji iny of claims 3 to 5, wherein the i
ither polvmerixable unsjIiu^i^at-aSi diohomer (e) contains a carbonyl ;?roup-eont aining polyniefiizablaili^Qsaturated monomer and^or a vinyl aromatic compound.
7* The ai watec-baiiiiiMl coating matirial Wifiurther contains a hydrazine
8. The method as desclfibedili iainy of claims 1 lo 7, wherein the
11 '■ I svat*3rba^ii!'i coating material (ll)ifurther contains at least one
1| \ i! I j '
compound salected fromlhe grctup consisting of nitrites, phytates, tannates, pliosphates anitpolyatniine compounds.
'11 ■ ■ j: i i
9. The method as described m iany of claims 1 to 8, wherein the
water-ba^ecl. coating matjerial (11) forms a coating film having a water
vapor penneability of 4(J> g/m^'|24ihr or less.
10. A (ioaiced article wlich fefcdated and Imished by the method as
I i' . i i i ■ described in any of clain|3 I to f J I

11. A coating finishing method substantially as herein described and exemplified.


223-CHE-2004 CORRESPONDENCE OTHERS 16-09-2011.pdf

223-CHE-2004 ENGLISH TRANSLATION 16-09-2011.pdf

223-CHE-2004 FORM-3 02-07-2012.pdf

223-CHE-2004 AMENDED CLAIMS 02-07-2012.pdf


223-CHE-2004 CORRESPONDENCE OTHERS 02-07-2012.pdf

223-CHE-2004 OTHER PATENT DOCUMENT 02-07-2012.pdf

223-CHE-2004 OTHER PATENT DOCUMENT 1 02-07-2012.pdf





223-che-2004-form 1.pdf

223-che-2004-form 26.pdf

223-che-2004-form 3.pdf

223-che-2004-form 5.pdf

Patent Number 253423
Indian Patent Application Number 223/CHE/2004
PG Journal Number 29/2012
Publication Date 20-Jul-2012
Grant Date 19-Jul-2012
Date of Filing 12-Mar-2004
Name of Patentee KANSAI PAINT CO LTD
Applicant Address 33-1 KANZAKI-CHO, AMAGASAKI-SHI, HYOGO-KEN 661-8555, JAPAN
# Inventor's Name Inventor's Address
PCT International Classification Number E04F13/12
PCT International Application Number N/A
PCT International Filing date
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 2003-69369 2003-03-14 Japan