CA1109343A - Method of metallic finishing - Google Patents

Method of metallic finishing

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Publication number
CA1109343A
CA1109343A CA305,343A CA305343A CA1109343A CA 1109343 A CA1109343 A CA 1109343A CA 305343 A CA305343 A CA 305343A CA 1109343 A CA1109343 A CA 1109343A
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CA
Canada
Prior art keywords
metallic
resin
coating material
thermosetting
parts
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
CA305,343A
Other languages
French (fr)
Inventor
Yoshio Imazaki
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kansai Paint Co Ltd
Original Assignee
Kansai Paint Co Ltd
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Filing date
Publication date
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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50Multilayers
    • B05D7/52Two layers
    • B05D7/53Base coat plus clear coat type
    • B05D7/532Base coat plus clear coat type the two layers being cured or baked together, i.e. wet on wet
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/06Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
    • B05D5/067Metallic effect
    • B05D5/068Metallic effect achieved by multilayers
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/60Additives non-macromolecular
    • C09D7/63Additives non-macromolecular organic
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/05Alcohols; Metal alcoholates
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31678Of metal
    • Y10T428/31688Next to aldehyde or ketone condensation product
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31678Of metal
    • Y10T428/31692Next to addition polymer from unsaturated monomers
    • Y10T428/31699Ester, halide or nitrile of addition polymer

Abstract

A B S T R A C T
A method of metallic finishing which comprises the steps of: applying a thermosetting liquid coating material to a substrate, further applying thereon a transparent thermo-setting powder coating material, and baking both coated films to cure them simultaneously. The above liquid coating material contains a film forming component of thermosetting resin and a pigment to give metallic appearance and the thermosetting resin component contains a cross liking agent of melamine formaldehyde resin which is modified with a monohydroxyl compound having a boiling point in the range of 150 to 250°C at 1 atm.
The obtained coating film is free from the defects of cratering, pinholing and the like and has quite excellent appearance such as metallic effect and high gloss.

Description

3~3 ~CKGROUND OF TH~ INVENTION
(1) Field of -the Invention This invention relates to a method of metallic finish-ing. More particularly, the invention relates to a method of metallic finishing to form the coating films which are excellent in surface appearance, especially in the smoo-thness and metallic effect of the coating films. The me-thod of the inven-tion com-prises two coating steps and one baking step (hereinafter re-Eerred to as "2 coat-l bake system").
(2) Description of Prior Art In recent years, powder coating materials containing no solvent have been widely employed and the utility thereof is rapidly expanded since they are advantageous in view of the prevention of environmental pollution. As the method for applying powder coating materials, the electrostatic spraying is generally employed, with which method it is possible to form a high build coating of more than 50 microns in thickness by a single coating.
Further, the recovery of scattered coating powder is so easy that the loss of coating material is small thereby affording economical advantages.
In the case of the powder coating material containing metal powder or both metal powder and coloring pigment, however, it is quite difficult to produce the metallic appearance like that of the conventional solvent type metallic coating material by the electrostatic spraying because the intensity of electric charge of metal powder is different from that of the film forming component of resin~ and the molten viscosity of the powder coat-ing material is high which results in the poor orientation of metal powder. Therefore, it has never been put into industrial practice.
In the case that a common solvent type thermosetting coating material containing metallic powder is first coated, ., , , :

~ transparent ther~osetting coating ,m,aterial is then coated and after that, the coated films are cured. In such 2 coat~
bake system, several surface defects such as gushiny (pinholing by solvent popping, cratering and the like, hereinafter referred to as "gushing"), surface roughness caused by poor levelling, unevenness of metallic effect and dulling of gloss are caused to occur, which are believed to be caused by the solvent of the solvent type thermosetting coating material remaining the coating film and the by-product of thermal curing reaction. Therefore, the 2 coat-l bake system of such coating materials are not accepted in the practical industries.
Further, there are proposed some relevant mekhods in the technical references, which will be described in the following.
In the method described in Published Unexamined Japanese Patent Application No. 51-87545 (1976) filed by Ford Motor Co., a base coat of aqueous coating material containing aluminium powder is first applied and it is cured at 107C for 10 minutes. An acry~ic powder coating material (clear) is then applied and cured at 177C for 25 minutes, thereby obtaining a coating film having good metallic appearance. The aqueous coating material is of acrylic type which is cured with a specific melamine resin (hexakis methoxymethyl melamine) and the powder coating material (clear) is glycidyl functional type acrylic resin which is cured by a dibasic acid. Since the above cited method is based on 2 coat-2 bake system and another type of alcohol is used in modifying,the melamine resin, No. 51~87545 is ~different from the present invention.
In the method described in Published Unexamined Japanese Patent Application No. !;1-115545 (1976) filed by Kansai Paint Co., Ltd., the substrate material is firstly degreased and subjected to phosphate conversion treatment. Then, it i5 applied with an anticorrosiv0 primer by electrodeposition and a intermediate coating material as a surfacer. Further, it i6 applied with a non-aqueous dispersion resin coating material containing aluminium powder (base coat) and settled for 4 minutes at room temperature. After that, an acrylic powder coatin~ meterial (clear) is applied thereto and baked at 180C for 20 minutes, thereby obtaining a coating film havi.ng good metallic effect.
The non-aqueous dispersion resin coating material used in tnis . method is acrylic type one con-taining a curable component of lS butylated melamine resin and the powder coating material is based on an acrylic resin of glycidyl functional type which is cured by dibasic acid. .
In Published Unexamined Japanese Patent Application No. 51-117733 (1976) filed by the same applicant is discloc.ed a similar method to No. 51-115545 except that the acrylic powder coating material contains a small quantity of coloring pigment.
In the disclosure of Published Unexamined Japan~.se Patent Application No. 51-130439 (1976) ~iled by Kansai Paint Co., Ltd. a substrate material is applied with a water-soluble an~/or water-dispersible coating material (base coat) containing metal powder and it is further applied with acrylic or polyester powder coating materia:l (clear, a small quantity of coloring pigment . may be contained). After that, both the coating films~are . simultaneously cured to form a coating having good metallic appearance. In this method, the water-soluble or water-dispersible 'l'l~D~ .3 acrylic resin or polyester resin in the bare coat is cured by water-soluble or water-dispersible melamine resin, benzoguanamine resin or urea resin.
There is another relevant reference, Published Unexamined ~apanese Patent ~pplication No. 52-69446 ~1977) da-ted June 9, 1977 and filed by Kansai Paint Co., Ltd.
In the method of this reference, a solvent type thermosetting . coating material containi ~ metal powder (base coat) is applied A to a substrate material~then the content of volatile matter in the coating film is reduced to 6% by weight or less by heating at 170C, for 10 minutes. A transparent thermosetting power coating material is then applied over that and both the coating films are simultaneously cured by baking to form a finished coating film having good metallic appearance. Thus, No. 52-69446 discloses substantially the same method as 2 coat-2 bake system.
In these methods described in the abo~,e references, nowever, there remains still several disadvantages. For example, the technical contents of Nos. 51-87545 and 52-69446 are directed to a 2 coat-2 bake system, in which system it `is impossible to keep dust and the like from sticking to a coating film of the base coat because of carrying out a bake oper~tion previous to a topcoat application process.
consequence, the resultant finishing aspect would often degrade.
Also in Nos. 51-115545, 51-117733, and 51-130439, as measurès to prevent gushing, properties of the topcoat resin can not help,being relied on. Therefore, in these prior arts there is a defect that the resins which they can u~.e are substantially limited taking ~ weathering resistance thereof into .0 consideration.

5 _ BRIEF SUMMARY OF THE INVENTION
In order to solve the above-described problems and to eliminate the disadvantages, the present in~entor has carried out wide and extensive investigations.
As the result, the present invention has been accompllshed~
in which, in the 2 coat-l bake system combinedly using a thermosetting liquid coating material containing metal powder, and a transparent thermosetting powder coating material, the thermosetting liquid coating material contains a cross linking agent of melamine formaldehyde resin which is modified with a specific monohydroxyl compound.
It is, therefore, the primary object of the present invention to provide an improved method of metallic finishing which is free from the defects of gushing, surface roughness, unevenness of metallic appearance or the like.
It is another object of the present invention to provide a m~thod of metallic finishing with which quite excellent metallic finishinq having good appearance such as metallic effect, thigh gloss, high film-build and the like can be obtained.
It is a further object of the present invention to provide a method of metallic finishing which can be put into practice without difficulty'and at low cost.
In accordance with the present invention, the mèthod of metallic finishin~ comprises the steps of: applying a thermosetting liquid coating material (hereinafter referred to as "base coat") to a substrate, ~hen applying a transparent thermosetting powder coating material-(hereinafter referréd to as "top coat") to the above coated surface, and baking both ~ tbe coat films to cure them slmultaneous1y.

l ~

D~3~3 The above liquid coating material contains a film forming component of thermosetting resin and a pigment for yiving metallic appearance to the finished coating and the -thermoset-ting resin component contains a cross linking agen-t of melamine formaldehyde resin which is modified with a monohydroxyl compound having a boiling point in the range of 150 to 250C at 1 atm.
DETAILED DESCRIPTION OF THE INVENTION
The monohydroxyl compounds which are used for modifying ¦
the melamine formaldehyde resin are aliphatic monohydric alcohols, aromatic monohydric alcohols, alicyclic monohydric alcohols, glycol monoalkyl ethers and glycol monoalkyl esters having boiling points of 150 to 250C at 1 atm. Exemplified as typical ones are:
b.p. (C) at 1 atm.
~15 l-hexanol (or n-hexanol) 158 cyclohexanol 161 l-heptanol 177 2-heptanol 160
3-heptanol 156 benzyl alcohol 205 methyl cyclohexanol (0) 165, l-n-octanol 195 2-n-octanol 178 2-ethylhexanol 183 phenyl methyl carbinol 204 l-nonanol 2i4 2-nonanol 198 3,3/5-trimethyl cyclohexanol-l 198 l-decanol (or n-decyl alcohol) 232 2-decanol 217 ..

I

l'l"~D ~3~,~

l-undecanol 2~7 2-undecanol 228 2,6,8-trimethylnonyl-4-alcohol 225 ethylene glycol monobutyl ether 171 ethylene glycol monohexyl ether 208 ethylene glycol monooctyl ether 228 ethylene glycol monophenyl ether2~0 - 2~8 diethylene glycol monomethyl et~er193 diethylene glycol monoethyl ether195 - 202 diethylene glycol monobutyl ether230 ethylene glycol monoacetate 182 As the modifying agent for the melamine formaldehyde resin of the base coat, when a monohydroxyl compound having a boiling point below 150C at 1 atm. is used, the evaporation ~ 15 of the monohydroxyl compound which is liberated by the reaction between the functiona] groups (described later) and the modified m~lamine formaldehyde resin is caused to occur abruptly, therefore, ~e gushing is brought about even in the coating film of top coat, and the metallic effect and the gloss of the obtained coating film become worse. On the other hand, when the monohydroxyl compound having a boiling point above 250C is used, the rate of curing by baking becom~s 610w and much monohydroxyl ~ompound which is liberate~ in the curing reaction remains in the coating film after the baking~
so that the hardness of the obtained coating film becomes low.
In addition, owing to the above facts, the solvent resistance of coating film also becomes worse. In the case that the monohydroxyl compounds having boiling points in the range of 150 to 250C are employed, the evaporation to the outside of coating film~ of the free monohydroxyl compound formed in the curing '., , . , ~.
.

3~3~13 reaction can be brought about gradually at an adequate rate during the baking after the application o~ the top coat.
Therefore, the metallic coating having quite desirable properties of metallic effect, high gloss and agreeable touch can be obtained without causing the gushing.
In the general preparation method for obtaining the melamine formaldehyde resin using the above monohydroxyl compound hav.ng a boiling point of the above described ran~e as the modifying agent, the reaction of the first s~ep is carried out by using 2 to 8 moles of formaldehyde and ~ to 15 moles of monohydroxyl compound per l mole of melamine. The conditions for the reaction are, for example, 1.5 to 3 hours at 80 to 100C. Then, a low boiling point hydrocarbon solvent ~ such as n-hexane, n~heptane or cyclohexane, is added to the reaction system as an auxiliary dehydrating agent so as to promote l the dehydration reaction, and after that, the hydrocarbon t f~ are ~rorn th~
solvent and excess monohydroxyl compound ~ removed-fromt-~e reaction system under a reduced pressure.
In this reaction, if desired, an amino compound having an active hydrogen joined to a nitrogen atom, for example, a triazine compound such as benzoguanamine, and urea can be used in place of the melamine. Further;, as the formaldehyde ` , the aqueous solution of formaldehyde and alcoho1 solution of formaldehyde which are commonly soled as formalin, and paraformaldehyde can be used.
As described above, the thermosetting resin in the base coat contains a modified melamine formaldehyde resin as a cross linking component. The functional resin which is combined with the modified melamine formaldehyde resin may be any of the functional resins which are used for the common baking ^11'!3~3~ 3 coating material of solvent type or dispersion resin type, as as they react with -the melamine formclldehyde resin when heated.
Exemplified as the functional resins of this kind ~hicn are . suitable for the use in the base coat of the present invention, are hydroxyl group functional acrylic copol~mer resins of organic solvent type, aqueous sol.ution type, non-aqu~ous dispersion type or aqueous dispersion type (or emulsion type), non oil or oil (or :Eatty acid) modified alkyd resins or polyester resins of organic solvent type, aqueous solution type or aqueous dispersion type, and epoxy resin esters of organic solvent type, a~ueous solution type or a~ueous dispersion type.
. The examples of the pigments which is mixed into the base coat of the present invention in order to give the metallic appearance of coated surfaces, are the metallic p lg ~ fs p~mgnct3 or non-metallic pigments of fine flakes, leaves or flinders. Exemplified as such pimgnets are aluminium powder (leafing type or non-leafing type), bron~e powder, copper powder, mica powder, treated mica powder (the mica powder deposited with a thin film of, for example, titanium oxide) and micaceous iron oxide. The compounding ratio of these pigments may be genera.lly in the range of 3 to 30 parts (by weight, the same shall apply hereinafter) to lOO parts of ~ thermosetting resin (as solid content) of the film forming component.
Further, besides the above pigments to impart metallic appearance, other components which are commonly use~ for coating materials, for example, coloring agents such as . inorganic pigments, organic pigments and oil-soluble dyestuf~s, and other additives such as dispersing agents, curing accelerators and surface levelling agents may also be added to .

~ J

the base coat of the present invention.
The base coat having the composition described abo~e can be prepared quite easily by adding ana c1ispersiny pigments and other components in accordance with t:he conventlonally known process or method.
The top coat of the present invention contains, as the main component, the powder o~ thermosetting resin. The resin powder, if not a self-curaDle resin, may con~ain a cross-linking ayent or curing agent. Further, it aan be compounded wi-th coloring agents and other additives. In view of the physical properties and weather resistance, the composition mainly composed of thermosetting acrylic resin or thermosetting polyester resin, is generally preferred. In the present ~ invention, however, the component is not restricted to the above resins.
In the preparation of the top coat by using for example a thermosetting acrylic resin, a vinyl monomer having glycidyl groups or hydroxyl groups such as glycidyl methacrylate, glycidyl acrylate, hydroxyethyl acrylate or hy~roxyethyl methacrylate, is used as the functional monomer, and the alkyl ester o~ acrylic acid or methacrylic acid or styrene as a nonfunctlonal monomer.
They are copolymerized by well known copolymerization process to obtain a copolymer resin ha~ing a glass transition temperature of 50 to 80C. To this copolymer, a polycarboxylic acid, blocked isocyanate compound or modified melamine resin is added as a component of curing agent, and if desired, a surface levelling agent and a cissing controlling agent are added to the composition. Then it is subjected to the well known powder making process which comprises the steps of, for example, mixing, melting, kneading, cooling, pulverizing and classifying.

:l~IL'.1~3~3 ~ f desired, a coloring agent or agents can be added to the top coat of the present intention. In the preparation o~ a transparent colored top coat, the common organic pigment, inorganic pigment or oil-soluble dyestuff can be used and the quantity of the coloring agent must be controlled within such range that, when the top coat is applied over th~ base coat, the metallic appearance o~ the flnished coating is not mpaired .
The practice of the method of the present invention will be exemplified in the following.
The viscosity of a base coat is adjusted to 10 to 30 seconds (Ford cup #4 at 20C, this shall apply hereinafter) by using a predetermined diluent. By air spraying or electrostatic spraying, the base coat is applied to the surface of a substrate (for example, a surface treated steel sheet, aluminium sheet, etc.) or a substrate which is previously supplied with a primer, thereby forming a coating film of 10 to 4~ microns in dried thickness. The coated substrate is then settled for 30 seconds to 30 minutes at an ordinary temperature, o~ if necessary, it is heated to about 100C for several minutes.
After that, the top coat is applied to the coated substrate by electrostatic coating method so as to form a 50 to 150 microns thickness of film when measured after the baking. The baking is done at a temperature of 150 to 200C for 10 to 45 minutes, in which both the coating films of base coat and top coat are simultaneously cured. By the above procedure, the metallic finish of the present invention ha~ring excellent smoothness and metallic gloss can be attained.
By using the modified melamine formaldehyde resin as an indispen~:able component of the base coat of the present - l2 -t~ 3'13 invention as described above, the appearance of mekallic finish coating in the two-coat one-bake system can be markedly improved . without causing the defects of gushing, surface roughness and î~ unevenness of metallic effect of the coating film but the smoothness of the obtained coating film is9q~e good.
In the following, the present invention will be further described in detall wlth ref~rence to several examples and comparative examples. In the examples, the term parts and %
are by weight unless otherwise indicated.
Example (A) Preparation of modified melamine formaldehyde resin solution A
A flask equipped with a stirrer was fed with 126 parts of melamine, 550 parts of 37% aqueous solution of . formaldehyde, and 1000 parts of ethylene glycol monobutyl ether, and the contents were heate~. at 90C for 2 hours. Then, 100 parts of n-heptane and 0.3 part of phthalic anhydride were added to the reaction system and the reaction temperature was raised to perform dehydration under refluxing for 3 hours.
After th~t, the n-heptane and excess ethylene glycol monobutyl ether were removed under a reduced pressure until the non-volatile matter in the system became 50%. The characteristic values of the obtained resin solution were a non-volatile matter of 50%, acid value of less than 1, viscosity of F - G (by Gardner bubble viscometer) and mineral spirit allowance of 10 - 20.
(B) Preparation of base coat A
As a dispersion stabilizer~, 210 % of a grafted product of poly-1,2-hydroxystearic acid and methacrylic acid copolymer was used to a mixture of vinyl monomer consisting of 30% of styrene, 30% of methyl methacrylate, 23% of 2-ethylhexyl acrylate, 15~
of hydroxyethyl acrylate and 2% of acrylic acid, thereby preparing ..

~ non-a~ueous dispersion resin in n-heptane The resln content of this resin dispersion was 60% and the degree of dispersion was 20~. By using this non~aqueous dispersion resin and ~he modified melamine formaldehyde resin solution A of the item (A), a base coat A containing 60% non-volatile matter was prepared according to the following formula, in which powdered aluminum paste was dispersed.
B~se Coak A Parts Non-aqueous dispersion resin (in n-heptane) 125 Modified melamine formaldehyde resin solution A 50 Non-leafing type powdered aluminum paste 12 (trademark: Aluminum Paste #1109 MA, made by Toyo Aluminum Co., Ltd.) 1~7 parts (C) Preparation of top coat A
A three neck flask equipped with a stirrer and a reflux condenser, was fed with 20 parts of styrene, 43 parts of methyl methacrylate, 18 parts of n-butyl acrylate, 3 parts of ethyl acrylate, 13 parts of glycidyl methacrylate, 3 parts of hydroxy-~thyl methacrylate and 100 parts of toluene, and further adding 1.5 parts of benzoyl peroxide to the flask, the contents were heated to 90 to 100C. After maintaining that temperature for 3 hours, 2 parts of benzoyl peroxide was further added and the reaction system was held at the above temperature for further
4 hours, thereby completing the copolymeri~ation. Then a cooling pipe was attached to the flask in order to remove the condensed solvent outside the flask and the heating was continued at an outside temperature of 120 to 140C with stirring to remove about 60~ of the toluene. After that, the pressure in the flask was reduced to 200 mmHg and the outside temperature was raised to 140 to 150C to remove the remaining toluene completely. The thus obtained copolymer was cooled, solidified and pulverized to fine .. . . ..

particles (a particle size ~E 6 mesh) b~ using a pulveri~er.
As the result, acrylic resin powder A was prepared.
Top coat A Parts Acrylic resin powder A 100 Decane dicarboxylic acid 13 Surface leveling agent (trademark: Modaflow, made by Mitsubishi Monsanto Chemical C.? __ _ 114 parts The mixture oE -the above formula was fused and kneaded at about 100C for 10 minutes by using a heating roller. Then it was cooled and pulverized into fine powder of 20 to 100 microns in particle size to obtain the top coat A.
(D) Coating Steel sheets (size: 300 x 90 x 0.8 mm, spec: JIS
G 3310, treated with zinc phosphate) were applied with an epoxy ester resin electrodeposition primer (trademark: Electron No.
1200, made by Kansai Paint Co., Ltd.). The base coat A which was adjustedto have a viscosity of 14 seconds was applied to the above coated surfaces with using an air spray gun (trade-20 make: Devilbiss JGA 502) to form coating films of 15 to 25 microns in dried thickness of the base coat A. The coated steel sheets were settled for about 5 minutes at room temperature, then the top coat A was applied to the surface of the coated steel sheets to form coatings of 60 to 80 microns thickness after baking by using an electrostatic spraying gun (trademark:
Stajet, made by Sammes Inc., France) at an electric charge of -80KB. Then, the coated steel sheets were baked in an oven at 170C for 20 minutes so as to cure both the coating layer sim-ultaneously. The thus obtained coatings were quite excellent without gushing, yellowing and orange peel, and the metallic effect and the gloss of the coatings were quite good. The results of tests are shown in the following Table 1.

3~3 Comparative Example 1 (A) Preparation o~ base coat B
The same non-a~ueous dispersion resin as that of (B) of Example 1 was used for the preparation of a base coat B of the following formula.
Base coat B Parts Non-aqueous dispersion resin (in n-heptane) 125.0 n-butanol modified melamine formaldehyde 41.7 resin varnish(trademark: Melan 28 containing 60% of non-volatile matter, made by ~itachi Chemical Industry Co., Ltd.) Non-leafing type powdered aluminum paste 12.0 (Aluminum Paste ~ 1109 MA) 178.7 parts (B) Coating The same surface treated steel sheets as -those in (D) of Example 1 were coated with the same electrodeposition primer, and in like manner as the coating method of (D) of Example 1, the above steel sheets were further applied with the base coat s which is followed by settling for 5 minutes at room temperature.
Then, the top coat A (cf. Example 1, (C)) was applied to the above steel sheets and the coated films were cured by baking. The gushing was caused to occur in the obtained coating films and the gloss was low, and further, the l ~l metallic efect was inferior. The test results thereof are shown in the following Table 1.
Example 2 (A) Preparation of top coat B
Mixed monomers of 20 parts of styrene, 25 part~ of methyl methacrylate, 15 parts of n-butyl acrylate, 15 parts of ethyl acrylate and 25 parts of hydroxyethyl methacrylate were copolymerized in like manner as (C) of Example 1, to prepare acrylic resin powcler B.
By using this resin, a top coat B was prepared in accordance with the method of (C) of Example 1 with the following formula:
Top coat B parts Acrylic resin powder B 65 Blocked isocya~ate curing agent 35 (trademark: Adduct s-1870, made by Veba Co., West Germany) Surface levelling agent (Modaflow) 101 parts (B) Coating Surface treated steel sheets were applied with,the same electrodeposition primer as that of (D) of Example 1 and they were furt~,er applied with the base coat A(cf. (B) of Example 1) in like manner as (D) of Example 1, thereby forming the coating films of base coat A of 30 to 40 microns in dried thickness. The coated sheets were then settled for 5 minutes and they were further applied with the top coat B by electrostatic coating. Both the coating layers were then cured simultaneously by baking at l70C for 25 minutes. ~ he. th~s obtained coating films were free from gushing, yellowing and orange peels, while the metallic effect and the gloss were quite good. The test results of these coating films are shown in the following Table 1.
Example 3 (A) Preparation of base coat C
Mixed monomers of 15 parts of styrene, 20 parts of methyl methacrylate, 30 parts of ethyl acrylate, 21 parts of n-butyl methacrylate, 12 parts oE 2~hydroxye~hyl methacrylate and 2 parts of acrylic acid were copolymerized in xylene with using ~,~'-azobisisobutyronitrile as a polymerization initiator to obtain a 50~ soluti.on of acrylic resin. By using this resin solution, a base coat C was prepared with the following formula:
Base coat C Parts . 50% acrylic resin solution 160 lS Modified melamine formaldehyde resin solution A 40 (cf. (A) of Example 1) ~/~ m/~v Non-leafing type powdered ~ ~*~ paste12 (aluminum Paste #1109 MA,) Z12 parts (B) Coating Su.rface treated.steel shee-ts were applied with the same electrodeposition primer as that of ~D) of Example 1 and they were further applied with the base coat C in like manner as (D) of Example 1 to form coating films of the base coat C of 25 to 35 microns in dried thickness. The coated surfaces were than heated to.100 + 10C for 5 mlnutes in a oven. After that, the top coat A (cf. (C) of Example 1) was . applied to the coated surfaces in like manner as the ~oating method of (D) of Example 1 and baked at 170C for 20 minutes.
~ he obtained coating films were free from the defects , ::

3~3 of gushing, yellowing and orange peels, and were excellent in the metallic effect and gloss. The test results of them are shown in the following Table 1.
Comparative Example 2 (A) Preparation of base coat D
A base coat D was prepared accordiny to the following formula:
Base coat D Parts 50% acrylic resin solution 160 (cf. (A) of Example 3) n-Butanol modified melamine forma].dehyde ; 33 .,.,..... resin varnish (Melan 28) A ~ a/u/~n/nc~
Non-leafing type powdered aLum~ti~ paste 12 ~Aluminum Paste #1109 MA,) 205 parts (B) Coating Surface treated steel sheets were applied with the same electrodeposition primer as that of (D) of Example 1 and they were fu~ther applied with the base coat D in like manner as (D) of Example 1. After that, they were settled for
5 minutes at room temperature. Then, the top coat A (cf. (C) of Example 1) was applied to the coated surfaces and the coating films were baked at 170C for 20 minutes. The obtained coating films suffered gushing and the gloss thereof was low, further, the metallic efect of the coating films was worse. The rest results of these coating films are shown in the following Table 1.
Example 4 (A) Preparation of base coat E
Base coat E Parts Acrylic resin emusion 111.1 11~3~3~' :3 (trademark: Almatex XV, non-volatile matter: 45 %, Toatsu Chemicals, Inc.) Water-soluble acrylic resin varnish 60.0 (trademark: Almatex XV-WC, non-volatile matter:
50~, made by Mitsui Toatsu Chemicals, Inc.) Modified melamine formaldehyde resin solution ~ 40.0 (cf. (A) of Example 1) f~ /U in I r~~
~A Non-leafing type powdered ~m~e~m paste 12.0 ~Aluminum Paste #1109 MA,) Ethylene glycol monohutyl ether 6.0 Diethylene glycol monobutyl ether 6.0 235.1 parts The base coat E was prepared in accordance with the above formula. The base coat E was a water thinnable . ~4IQ~;I~ ~er type and contained 49~ of non-bol~t-~le--ma-te-r~
(B) Coating Surface treated steel sheets were applied with the same electrodepositi.on primer as that of (D) of Example 1. The base coat E was reduced to ~ viscosity of 26 seconds by using a thinner consisting of 80 parts of deionized water and 20 parts of diethylene glycol monobutyl eth~.r. The thinned base coat E was applied to the above steel sheets to form coating films o~ 15 to 25 microns in dried thickness by using an air spray gun (trademark: Devilbiss JGA 502) in a coating booth of a temperature of 25C and a relative humidity of 50~. The coated steel sheets were settled at room .
temperature for 5 to 10 minutes, af-ter that, the top coat A
(cf. (C) of Example 1) was applied to the coated surfaces of the steel sheets by means of electrostatic spraying under the same conditions as those of (D) of Exa~ple 1. Both the coating .. .

~ 3~

films were simultaneously cured by ba]cing at 170C for 20 minu-tes.
The obtained coating films were free from the defects of gushing, yellowing and serious orange peels, and the metallic effect and gloss of the coating films were quite good. The test results thereof are shown in the follow.ng Table 1.
Comparative Example 3 (A) Preparation of base coat F
Base coat F Parts Acrylic resin emulsion 111.1 (Almatex XV) Water-soluble acrylic resin varnish 60.0 (Almatex XV-WC) Methanol modified melamine formaldehyde 28.6 ~ resin varnish (trademark: Sumimal M-62W, non-volatile matter: 70%, made by Sumitomo Chemical Co., Ltd.) ~ aiu ~;~v A Non-leafting type powdered ~mini~ paste12.0 (Aluminu~ Paste #1109 MA) Isopropyl alcohol 12.0 According to the above formula, the base coat F
was prepared, which contained 48~ of non-volatile matter and could be diluted with water.
(B) Coating Surface treated steel sheets were applied with the sam~ electrodeposition primer as that of (D) o~ Example 1 In accordance with the coating method of (B) of Example 4, the base coat F was applied to the surfaces of the abo~e steel sheets and the coated steel sheets were settled for 30 5 to 10 minutes at room temperature. Th~n the top coat A

, 1'~ 3 ' 3 (cf. (C) of Example 1) was applied to the coated steel sheets by means of electrostatic coatlng and -the baking was carried out at 170C for 20 minutes. In 1:he coatlng films thus obtained, gushing and yellowing were caused to occur, and the metallic effect and gloss were inferior. The test results thereof are shown in the following Table 1.
Example 5 (A) Preparation of modified melamine formaldehyde resin solution B
By using 126 parts of melamine, 550 parts of 37%
formaldehyde aqueo~s solution and 1000 parts of diethylene ylycol monobutyl ether, reaction was performed in like manner as (A) of the foregoing Example 1 to obtain a modified melamine formal-dehyde resin solution B containing 50~ of non-volatile matter.
(B) Preparation of base coat G
According to the following formula, a base coat G
was prepared.
Base coat G parts 50% acrylic resin solution (cf. (A) of 160 Ex~mple 3) Modified melamine formaldehyde resin solution B 40 a l u w~
Non-leafing type powdered ~*}~L~ paste 12 (Aluminum Paste #1109 MA) ' 212 parts (C) Coating 2S Surface treated steel sheets were applied with the same electrodeposition primer as that of (D) of Example 1, In accordance with the coa-ting meth~d of (D) of Example 1, the base coat G was applied to the above steel sheets to form coating films of 20 to 30 microns in dried thickness.
They were then settled for 5 minutes at room temperature '33a~3 and after that, the top coat A (cf. (C) of Example l) was applied to the steel sheets and baked at 170C for 20 minutes.
The obtained coating films were Eree from the defects of gushin~, yellowing and serious orange peel, and the metallic effect an~ gloss of the coating films were quite good. The test results thereof are shown in the following Table l.
Comparative 13xample 4 (A) Preparation of rnodified melamine formaldehyde resin solution C
By usinc~ 126 parts of melamine, 550 parts of 37~
formaldehyde a~ueous s~lution and lO00 parts of tridecanol (b.p.at l atm.:about 270C), reaction was carried out in like manner as(A) of the foregoing Example l to obtain a modified melamine formaldehyde resin solution C containing 50% of non-volatile matter.
. (B) PreparatiGn of base coat H
In accordance with the following formula, a base coat H was prepared.
Base coat H Parts 50% acrylic resin solution 160 (cf. (A) of Example 3) Modified melamine formaldehyde resin solution C 40 al~ ~~
Non-leafin~ type powdered a}~=t~ffffl paste 12 tAluminum Paste #llO9 MA) 212 parts (C) Coating Surface treated steel sheets were applied with the same electrodeposition primer as that of (D) of Example l.
In accordance with the coatiny method ~f (D) of Example l, the base coat H was applied to the above steel sheets to form coating films of 20 to 30 microns in dried thickness.
They were then settled for 5 minutes at room temperature and ~ 3 after that, the top coat A (cf. (C) of Example ].) was applied to the steel sheets and baked at 170~C fcr 20 minutes. In connection with the obtained coating, even though gushing was not caused to occur, the metallic effect,solvent resistance and physical properties (especia.lly the hardness) of the coating films were worse. The test res~llts of the coating Eilms are shown in the followlng Table 1.
Example 6 (A) Preparat.ion of modified melamine formaldehyde resin solution D
sy using 126 parts of melamine, 550 parts of 37% formaldehyde aqueous solution and 1000 parts of l-nonanol, reaction was carried out in like manner as (A) of the foregoing Example 1 to obtain a modified melamine formaldehyde resin solution D containing 50% of non-volatile matter.
(B) Preparation of base coat I
In accordance with the following formula, a base coat I was prepared.
Base coat parts 50% acrylic resin solution 160 (cf. (A) of Bxample 3) Modified melamine formaldehyde resin solution D 40 . ~ Non-leafing type powdered ~m~fl~m paste12 (Aluminum Paste #1109 M~) 212 parts (C) Coating Surface treated steel sheéts were applied with the same electrodeposition primer as that of (D) of Examp1e 1.
. In accordance wi.th the coati.ng method of (D) of Example 1, the base coat I was applied to the above steel sheets to form ~ ~oating f ms of 20 to 30 micr ns in dried thicknes~. They were ~ 3~3 then settled for 1 minute at room temperature and after that, the top coat A (cf. (C) of Example 1) was applied to -the steel The th~s sheets and baked at 170C for 20 minutes. ~*~ obtained coating films were free from the defects of gushing, yellowing and serious orange peels, and the metallic effect and gloss of the coating films were quite good. The test results thereof are shown in the following Table 1.
Example 7 (A) Preparation of modified melamine formaldehyde resin solution E
By using 126 parts of melamine, 550 parts of 37~
formaldehyde aqueous solution and 1000 parts of l-undecanol, the reaction just like that of (A) of Example 1 was performed.
Thereby, a modified melamine formaldehyde resin solution E
c:ontaining 50% of non-volatile matter was prepared.
(B) Preparation of base coat J
According to the following formula, a base coat J
was prepared.
Base coat J Parts 50~ acrylic resin solution 160 (cf. (A) of Example 3) Modified melamine formaldehyde resin solution E 40 al~ m~
Non-leafing type powdered ~a~ Y~ paste12 (Aluminum Paste #1109 MA) 212 parts (C) Coalingi Surface treated steel skeets were applied with the same electrodeposition primer as that of (D) of Example 1-. In accordance with t~e coating method of (D) of Example 1, the base coat J was applied to the above steel sheets to form coating films of 20 to 30 microns in dried thickness. They were then .
, :- ~ 3~ 3 settled Eor 10 minutes at room temperature and after that, the top coat A (cf. (C) of Example 1) was applied to the steel sheets .~ rhe, ~hu~ .
.~ and baked at 170C for 20 minutes. ~ obtained coating films were free from the defects of gushing, yellowing and serious o r C~ v~ ,c~3 ~
S ~e peels, and the metallic effect and gloss of the coatiny films were quite good. The te.st results thereof are shown in the following ~able 1.
Exarnple (A~ Preparation of modified melamine formaldehyde resin solution ~ By using 126 parts of melamine, 550 parts of 37~
formaldehyde aqueous solution and 1000 parts of ethylene glycol monoacetate, the reaction was per~ormed in like manner as (A) of the foregoing Example 1 to obtain a modified melamine formaldehyde resin solution F containing 50% of non-volatile 15. matter.
(B) Preparation of base coat K
According to the following formula, a base coat K
was prepared.
Base coat K Parts 50~ acrylic resin solution 160 (cf. (A) of Example 3) Modified melamine formaldehyde resin solution F ' 40 ~ I ~ W~
Non-leafing type powdered a}u=~}~m paste 12 (Aluminum Paste #1109 MA) 212 parts (C) Coating ~ ' Surface treated steel sheets were applied with the same electrodeposition primer as that of (D) of Example 1.
In accordance with the coating method of (D) of Example 1, the base coat K was applied to the above steel sheets to .

1~3~3 form coating films of 20 to 30 microns in dried thickness. They were then settled fcr 5 minutes at room temperature and after that, the top coat A (cf. (C) of Example 1) was applied to -the p ~ ~ ~he ~ 5 steel sheets and baked at 170C for 20 minutes. ~ obtained coating films were free from the defects of gushiny, yellowing and serious orange peels, and the metallic effect and gloss of the coating films were cIuite good. Th~ test results of them are shown in the following Table 1.
In Table 1, the evaluation of the coating films was made with naked eyes. The standards for the evaluated symbols are as follows:
Good : No defect was found in the coating film.
Fair : Slight defect was found Poor : Defects were found apparently Bad : Defects of coating films were serious ~ 3~3 _ .
o ~ ol t ~i f ~ ~ ~ ~ ~ N ~ o ~ ~o ~ ~ " ¦ o ¦ ¦ N ~

~ _ . _ ~ _ --_ _ . ~ ,V~I~u ~ ~ ~ ~ ~ ~ ~n ~ ~ ~ r7 `,, O o ~ ,~C a~ ~¢ ~ ~¢ ~ ,~:C ~S ~¢ ~ ~¢ .,:

.4 ~: P~ ~ u n ~ ~ ~ ~ H I~ ~:; .
. ~. .__ _ . _ _ ~ ~ ~ ~`

Claims (10)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE PROPERTY
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A method of metallic finishing which comprises the steps of:
applying a thermosetting liquid coating material to a substrate, said liquid coating material containing a film forming component of thermosetting resin and a pigment for giving metallic appearance to the finished coating and said thermosetting resin component containing a cross linking agent of melamine formaldehyde resin modified with a monohydroxyl compound having a boiling point in the range of 150 to 250°C
at 1 atm., further applying thereon a transparent thermosetting powder coating material, and baking both coated films to cure them simultaneously.
2. The method of metallic finishing as claimed in claim 1, in which said monohydroxyl compound used for the modification of said melamine formaldehyde resin is at least one member selected from the group consisting of aliphatic monohydric alcohols, aromatic monohydric alcohols, alicyclic monohydric alcohols, glycol monoalkyl ethers and glycol monoalkyl esters having boiling points of 150 to 250°C at 1 atm.
3. The method of metallic finishing as claimed in claim 1, in which said thermosetting resin contains a functional resin component which is combined with said melamine formaldehyde resin, said functional resin component being at least one member selected from the group consisting of hydroxyl group functional acrylic copolymer resins of organic solvent type, non-aqueous dispersion type or aqueous dispersion type, non-oil or oil modified alkyd resins or polyester resins of organic solvent type, aqueous solution type or aqueous dispersion type and epoxy resin esters of organic solvent type, aqueous solution type or aqueous dispersion type.
4. The method of metallic finishing as claimed in claim 1, in which said pigment for giving metallic appearance is at least one member selected from the group consisting of aluminum powder, bronze powder, copper powder, mica powder, treated mica powder and micaceous iron oxide.
5. The method of metallic finishing as claimed in claim 1, in which 3 to 30 parts by weight of said pigment for giving metallic appearance is used to 100 parts by weight (as resin solid) of said film forming component of thermosetting resin.
6. The method of metallic finishing as claimed in claim 1, in which a coloring pigment or pigments are added to said thermosetting liquid coating material.
7. The method of metallic finishing as claimed in claim 1, in which said monohydroxyl compound is selected from the group consisting of ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, 1-nonanol, 1-undecanol and ethylene glycol monoacetate.
8. The method of metallic finishing as claimed in claim 1, in which said modified melamine formaldehyde resin is the reaction product of 2-8 mols of formaldehyde and 8-15 mols of said monohydroxyl compound per mol of melamine.
9. The method of metallic finishing of claim 1, in which said transparent thermosetting powder coating material comprises a copolymer of styrene, methyl methacrylate, n-butyl acrylate, ethyl acrylate and hydroxyethyl methacrylate and wherein said thermosetting liquid coating material comprises a resin of ingredients comprising styrene, methyl methacrylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate and acrylic acid, said pigment is powdered aluminum and said monohydroxyl compound is ethylene glycol monobutyl ether.
10. The method of metallic finishing as claimed in claim 1, in which said transparent thermosetting powder coating material comprises a copolymer of styrene, methyl methacrylate, n-butyl acrylate, ethyl acrylate, glycidyl methacrylate and hydroxyethyl methacrylate, said pigment is powdered aluminum, and said monohydroxyl compound is selected from the group con-sisting of ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, 1-nonanol, 1-undecanol and ethylene glycol monoacetate.
CA305,343A 1977-06-14 1978-06-13 Method of metallic finishing Expired CA1109343A (en)

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FR (1) FR2394591A1 (en)
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GB1597878A (en) 1981-09-16
DE2825884A1 (en) 1978-12-21
DE2825884B2 (en) 1980-08-07
US4220675A (en) 1980-09-02
IT7849818A0 (en) 1978-06-12
IT1105724B (en) 1985-11-04
FR2394591B1 (en) 1980-07-04
JPS544934A (en) 1979-01-16
FR2394591A1 (en) 1979-01-12
JPS6044027B2 (en) 1985-10-01

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